Compositions with enhanced flexibility

ABSTRACT

Compositions are provided which comprises an active hydrogen-containing resin, a flexibilizer and at least one curing agent. The cured compositions possess enhanced flexibility while maintaining hardness, and are highly suitable for applications such as coatings, adhesives, sealants, gaskets, industrial rubber goods, and the like.

This application claims priority to Provisional U.S. Patent ApplicationNo. 61/928,572 dated Jan. 17, 2014, the entire contents of which areincorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions that upon curing providecured compositions having enhanced flexibility. These compositions areuseful as coatings, adhesives, sealants and composites.

2. Description of Related Art

Resin compositions are useful as adhesives, sealants, composites, andespecially coatings. Current high surface hardness protective coatingstypically contain acrylic resins having high glass transitiontemperature (Tg), such as acrylic resins derived from methylmethacrylate and styrene monomers or alkoxysilane-modified acrylicresins, for example, acrylic resins incorporating(meth)acryloxyalkoxysilane, such as 3-methacryloxypropyltrialkoxysilane.While such acrylic-based coating compositions are useful in formingprotective coatings having a high hardness, the coatings formed tend tocrack after outdoor exposure for a period of time.

Accordingly, there is a continuing need for compositions having enhancedflexibility while maintaining hardness.

SUMMARY OF THE INVENTION

In accordance with one aspect of the invention, there is provided acomposition comprising:

(a) flexibilizer (i) having general formula (I):

wherein:

each occurrence of R¹ is independently an alkyl group having from 1 to 6carbon atoms, a phenyl group or an arenyl group having 7 to 12 carbonatoms;

each occurrence of R² is independently an alkyl group having from 1 to 6carbon atoms;

each occurrence of R³ is independently a phenyl group or an arenyl grouphaving 7 to 12 carbon atoms;

each occurrence of X¹ is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, or an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group;

each occurrence of X² is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group, or agroup with the formula (II):

wherein:

R¹, R² and R³ are the same as defined above;

-   -   each occurrence of subscripts a, b, c, d, e and f is        independently an integer wherein a is 1 to 3; b is 0 to 500, c        is 1 to 500, d is 0 to 10, e is 0 to 50, and f is 0 to 50 with        the provisos that    -   (1) the molar ratio of b to c is from 0:1 to 15:1, and    -   (2) the molar ratio of d to c is from 0:1 to 1:1;    -   (b) at least one active hydrogen-containing resin (ii) selected        from the group consisting of polyol (iii), amine-functional        resin (iv) and mercapto-functional resin (v); and,    -   (c) at least one curing agent (vi) selected from the group        consisting of isocyanate-containing compound (vii), blocked        isocyanate-containing compound (viii) and aminoplast (ix).

The present invention provides compositions having enhanced flexibilitywhile maintaining hardness. The compositions of the present inventionare especially useful for the manufacture of coatings, sealants,adhesives, gaskets, and the like.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the specification and claims herein, the following terms andexpressions are to be understood as indicated below.

It will also be understood that any numerical range recited herein isintended to include all sub-ranges within that range and any combinationof end points of said ranges or sub-ranges.

It is to be understood that the terminology used herein is for purposesof describing particular embodiments only and is not intended to limitthe scope of the present teachings which will be limited only by theappended claims.

Throughout the application, where a composition is described as having,including, or comprising specific components, it is contemplated thatsuch composition also consists essentially of, or consists of, therecited components.

The use of the singular herein, for example, “a,” “an,” and “the,”includes the plural (and vice versa) unless specifically statedotherwise.

In the application, where a component or material is said to be includedin and/or selected from a list of recited components or materials, it isto be understood that the component or material can be any one of therecited components or materials or any combination thereof.

The use of the terms “include,” “includes,” “including,” “have,” “has,”“having,” “contain,” “contains,” or “containing,” including grammaticalequivalents thereof, should be generally understood as open-ended andnon-limiting, for example, not excluding additional unrecited componentsor steps, unless otherwise specifically stated or understood from thecontext.

As used herein, the term “monovalent” in reference to a group means thatthe group is capable of forming one covalent bond per group.

As used herein, the term “hydrocarbon group” is a group consisting ofcarbon and hydrogen atoms and includes acyclic hydrocarbon groups,alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

As used herein, the term “acyclic hydrocarbon group” means any straightchain or branched hydrocarbon group, preferably containing from 1 to 60carbon atoms, which may be saturated or unsaturated. Suitable monovalentacyclic hydrocarbon groups include alkyl, alkenyl and alkynyl groups.Representative and non-limiting examples of monovalent acyclichydrocarbon groups are methyl, ethyl, sec-butyl, tert-butyl, octyl,decyl, dodecyl, cetyl, stearyl, ethenyl, propenyl, and butynyl. Suitabledivalent acyclic hydrocarbon groups include linear or branched alkylenegroups. Representative and non-limiting examples of divalent acyclichydrocarbon groups are methylene, ethylene, propylene, hexylene,methylethylene, 2-methylpropylene and 2,2-dimethylpropylene. Suitabletrivalent acyclic hydrocarbon radicals include alkanetriyl radicals,such as, for example, 1,1,2-ethanetriyl, 1,2,4-butanetriyl,1,2,8-octanetriyl and 1,2,4-hexanetriyl.

As used herein the term “alkyl” means any saturated straight or branchedmonovalent hydrocarbon group. In a preferred embodiment, monovalentalkyl groups are selected from linear or branched alkyl groupscontaining from 1 to 60 carbons per group, such as, for example, methyl,ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,pentyl, hexyl, heptyl, decyl and dodecyl.

As used herein the term “alkenyl” means any straight or branchedmonovalent hydrocarbon group containing at least one carbon-carbondouble bond and preferably containing from 2 to 10 carbon atoms, suchas, for example, ethenyl, 2-propenyl, 3-butenyl, 5-hexenyl and7-octenyl.

As used herein the term “arenyl” means any aromatic hydrocarbon group inwhich one or more hydrogen atoms have been substituted by the samenumber of like and/or different alkyl groups. In a preferred embodiment,arenyl includes 4-methylphenyl, 2,4-dimethylphenyl and2,4,6-trimethylphenyl.

As used herein, the term “alicyclic hydrocarbon group” means a groupcontaining one or more hydrocarbon rings, preferably containing from 3to 12 carbon atoms, which may optionally be substituted on one or moreof the rings with one or more monovalent or divalent acyclic groupcontaining preferably 1 to 6 carbon atoms. In the case of an alicyclichydrocarbon group containing two or more rings, the rings may be fusedrings in which the two rings share two or more carbon atoms in common,or rings that are bonded to each other through a covalent bond ordivalent acyclic group. Suitable monovalent alicyclic hydrocarbon groupsinclude, for example, cycloalkyl groups, such as cyclohexyl andcyclooctyl or cycloalkenyl groups, such as cyclohexenyl. Suitabledivalent hydrocarbon groups include, saturated or unsaturated divalentmonocyclic hydrocarbon radicals, such as, for example,1,4-cyclohexylene. Suitable trivalent alicyclic hydrocarbon radicalsinclude cycloalkanetriyl radicals such as, for example,1-ethylene-2,4-cyclohexylene and1-methylethylene-3-methyl-3,4-cyclohexylene.

As used herein, the term “aromatic hydrocarbon group” means ahydrocarbon group containing one or more aromatic rings, which may,optionally, be substituted on the aromatic rings with one or moremonovalent or divalent acyclic groups preferably containing 1 to 6carbon atoms. In the case of an aromatic hydrocarbon group containingtwo or more rings, the rings may be fused rings in which the rings sharetwo or more carbon atoms in common, or rings that are bonded to eachother through a covalent bond or divalent acyclic group. Suitablemonovalent aromatic hydrocarbon include, for example, phenyl, tolyl,2,4,6-trimethylphenyl, naphthyl and anthryl, as well as aralkyl groups,such as, for example, 2-phenylethyl. Suitable divalent aromatichydrocarbon groups include divalent monocyclic arene groups such as, forexample, 1,2-phenylene, 1,4-phenylene, 4-methyl-1,2-phenylene andphenylmethylene. Suitable trivalent aromatic hydrocarbon groups include,for example, 1,3,5-phenylene and 1,2,4-phenylene.

Flexibilizer (i)

Flexibilizer (i) is a polysiloxane compound represented by generalformula (I):

wherein:

each occurrence of R¹ is independently an alkyl group having from 1 to 6carbon atoms, a phenyl group or an arenyl group having 7 to 12 carbonatoms;

each occurrence of R² is independently an alkyl group having from 1 to 6carbon atoms;

each occurrence of R³ is independently a phenyl group or an arenyl grouphaving 7 to 12 carbon atoms;

each occurrence of X¹ is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, or an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group;

each occurrence of X² is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group, or agroup with the formula (II):

wherein:

R¹, R² and R³ are the same as defined above;

each occurrence of subscripts a, b, c, d, e and f is independently aninteger wherein a is 1 to 3; b is 0 to 500, c is 1 to 500, d is 0 to 10,e is 0 to 50, and f is 0 to 50 with the provisos that

-   -   (1) the molar ratio of b to c is from 0:1 to 15:1, and    -   (2) the molar ratio of d to c is from 0:1 to 1:1.

The repeat units of general formula (II) may be oriented in blocks orrandomly, and is generally a mixture of components with the structure offormula (II).

In certain embodiments of the composition of this invention, inflexibilizer (i) of formula (I), each occurrence of X¹ is independentlyhydroxyl, methoxy, ethoxy, propoxy or isopropoxy; R¹ is methyl orphenyl; R² is methyl; R³ is phenyl; b is 1 to 100; c is 2 to 100; d is0; and the molar ratio of b to c is from 0.5:1 to 10:1. Preferably, X¹is hydroxyl, methoxy or ethoxy; d is 0; and the molar ratio of b to c is2:1 to 7:1.

Specific examples of flexibilizers (i) includeHO—Si(CH₃)₂—O-[Si(CH₃)₂O]_(r)—[Si(Ph)₂O]_(s)—Si(CH₃)₂—OH where r/s is 4,CH₃O—Si(CH₃)₂—O—[Si(CH₃)₂O]_(u)-[Si(Ph)₂O]_(w)—Si(CH₃)₂—OCH₃ where u/wis 3, Ph is phenyl, or mixtures thereof.

In another embodiment, flexibilizer (i) of formula (I) has a silanolcontent or a SiX¹ content of from 2 to 15 mole %, and preferably from 5to 10 mole %, based upon the total number of silicon atoms anddetermined by ²⁹Si NMR spectroscopy. In still another embodiment,flexibilizer (i) has a weight average molecular weight of from 500 to50,000, preferably from 1,000 to 10,000, as determined in accordancewith DIN Standard 55672 (1) using polystyrene standards.

The amount of flexibilizer (i) of formula (I) that is used in thecompositions is from 1 to 50 parts by weight per one hundred parts ofactive hydrogen-containing resin (ii), more specifically from 1 to 30parts by weight per one hundred parts of such resin.

Active Hydrogen-Containing Resin (ii)

Active hydrogen-containing resin (ii) is at least one member selectedfrom the group consisting of polyol (iii), amine-functional resin (iv)and mercapto-functional resin (v).

(1) Polyol (iii)

In one embodiment, polyol (iii) is at least one member selected from thegroup consisting of acrylic polyol, polyether polyol, polyester polyol,polyetherester polyol, hydroxyl-terminated polybutadiene,hydroxyl-terminated polyurethane, polyesterether polyol and acrylicpolyol containing a alkoxysilyl group.

In one preferred embodiment, polyol (iii) is acrylic polyol containingan alkoxysilyl group.

Suitable polyols (iii) include poly(oxyalkylene)ether diols (i.e.,polyether dials), in particular, poly(oxyethylene)ether diols,poly(oxypropylene)ether diols and poly(oxyethylene-oxypropylene)etherdiols, poly(oxyalkylene)ether triols, poly(tetramethylene)ether glycols,polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides,polyhydroxy polythioethers, polycaprolactone diols and triols,polybutadiene diols, and the like, with number average molecular weights(Mn) between 500 and 25,000 grams per mole. The number average molecularweights are determined in accordance with DIN Standard 55672 (1) usingpolystyrene standards.

In one embodiment of the invention, suitable polyols (iii) arepoly(oxyethylene)ether diols with number average molecular weights (Mn)between 500 and 25,000 grams per mole. In another embodiment of theinvention, the polyols used in the production of activehydrogen-containing resin (ii) are poly(oxypropylene)ether diols withnumber average molecular weights between 1,000 and 20,000 grams permole. The number average molecular weights are determined in accordancewith DIN Standard 55672 (1) using polystyrene standards. Mixtures ofpolyols of various structures, molecular weights and/or functionalitiescan also be used.

The polyether polyols can have a functionality of up to 12, morespecifically a functionality of from 1.5 to 8 and even morespecifically, a functionality of from 1.8 to 2.2. Suitable polyols (iii)are the polyether polyols prepared in the presence of double-metalcyanide (DMC) catalysts, an alkaline metal hydroxide catalyst, or analkaline metal alkoxide catalyst; see, for example, U.S. Pat. Nos.3,829,505, 3,941,849, 4,242,490, 4,335,188, 4,687,851, 4,985,491,5,096,993, 5,100,997, 5,106,874, 5,116,931, 5,136,010, 5,185,420 and5,266,681, the entire contents of which are incorporated by referenceherein. Polyether polyols produced in the presence of such catalyststend to have high molecular weights and low levels of unsaturation,properties which are believed to account for the improved performance ofcompositions derived therefrom. The polyether polyols preferably have anumber average molecular weight of from 1,000 to 25,000 grams per mole,more preferably from 2,000 to 20,000 grams per mole and more preferablystill from 4,000 to 18,000 grams per mole. The levels of terminalethylenic unsaturation are generally less than 0.2, preferably less than0.02, and more preferably less than 0.008 milliequivalents per gram(meq/g) of polyol. Examples of commercially available diols that aresuitable for making polyol (iii) herein include, but are not limited to,ARCOL® R-1819 (number average molecular weight of 8,000 grams per mole,available from Bayer Material Science), E-2204 (number average molecularweight of 4,000 grams per mole) and ARCOL® E-2211 (number averagemolecular weight of 11,000 grams per mole, available from Bayer MaterialScience).

Among the hydroxyl-terminated polybutadiene representatives of polyol(iii) are those possessing a number average molecular weight of from 500to 10,000 grams per mole and advantageously from 800 to 5,000 grams permole, a primary hydroxyl group content of from 0.1 to 6.0milliequivalents per gram and advantageously from 0.3 to 1.8milliequivalents per gram, a degree of hydrogenation of from 0 up to 100percent of the olefinic sites present and an average content ofcopolymerized additional monomer(s) of from 0 up to 50 weight percent.

Hydroxyl-terminated polybutadienes of the above-described type,averaging more than one predominantly primary hydroxyl group permolecule, for example, averaging from 1.7 to 3 or more primary hydroxylgroups per molecule, are suitably employed herein. More specifically,the hydroxyl-terminated polybutadienes possess an average of at least 2,and advantageously from 2.4 up to 2.8, hydroxyl groups per molecule, thehydroxyl groups being predominantly in terminal allylic positions on themain, i.e., generally the longest, hydrocarbon chain of the molecule. By“allylic” configuration is meant that the alpha-allylic grouping ofallylic alcohol, i.e., the terminal hydroxyl groups of the polymer, arebonded to carbon atoms adjacent to double bonded carbon atoms.

The ratio of cis-1,4, trans-1,4 and 1,2-vinyl unsaturation which occursin the butadiene polymers employed in this invention, the number andlocation of the hydroxyl groups and the molecular weight of thebutadiene polymers will be influenced by the process employed for theirmanufacture, the details of which are known in the art.

Hydroxyl-terminated polybutadienes possessing these characteristics arecommercially available from several sources and are thereforeconveniently employed herein.

The useful hydroxyl-terminated polybutadienes herein can alsoincorporate one or more other copolymerizable monomers which can conferparticularly desirable properties upon the silylated polymers herein.The total amount of copolymerized monomer will not exceed, on average,50 weight percent of the hydroxyl-terminated polybutadiene copolymer.Included among the copolymerizable monomers are monoolefins and dienessuch as ethylene, propylene, 1-butene, isoprene, chloroprene,2,3-methyl-1,3-butadiene, 1,4-pentadiene, etc., and, ethylenicallyunsaturated monomers such as acrylonitrile, methacrylonitrile,methylstyrene, methyl acrylate, methyl methacrylate, vinyl acetate, etc.Alternatively or in addition thereto, the hydroxyl-terminatedpolybutadienes can be reacted with one or more other monomers to providehydroxyl-terminated block copolymers. Such monomers include 1,2-epoxidessuch as ethylene oxide and propylene oxide which will provide polyethersegments, e-caprolactone which will provide polyester segments, and thelike.

Hydroxyl-terminated polyurethane representatives of polyol (iii) can beprepared from the reaction of a stoichiometric excess, usually slightexcess, of one or more polyols such as any of those previously mentionedand one or more polyisocyanates such as any of those listed below,optionally together with one or more chain extenders in accordance withknown and conventional methods. Examples of suitable chain extenders arepolyhydric alcohols such as ethylene glycol, propylene glycol,propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,triethylene glycol, tetrathylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol and the like. Additionalpolyols can be chosen from polyols described above and include polyetherpolyols, polyester polyols, polyetherester polyols, polyesteretherpolyols, polybutadienediols, polyoxyalkylene diols, polyoxyalkylenetriols, polytetramethylene glycols, polycaprolactone diols and triols,and the like, all of which possess at least two primary hydroxyl groups.

In one embodiment, acrylic polyols representative of polyols (iii) canbe acrylosilane polymers obtained from the copolymerization of at leastone monomer selected from the group consisting of alkyl methacrylate,alkyl acrylate, each having from 1-12 carbon atoms in the alkyl group,isobornyl methacrylate, isobornyl acrylate, hydroxy alkyl acrylate, eachhaving from 1-4 carbon atoms, and styrene, and at least oneethylenically unsaturated silane monomer, e.g., ethylenicallyunsaturated silane monomer having the general formulae (III)-(V):

wherein:

R⁴ is methyl, ethyl, methoxy, ethoxy, propoxy or isopropoxy;

each R⁵ and R⁶ are independently hydrogen, methyl, ethyl, propyl orisopropyl;

R⁷ is hydrogen, methyl or ethyl;

R⁸ is an alkylene group having from 2 to 8 carbon atoms; and,

the subscript n is an integer of from 0 to 8.

In another preferred embodiment, active hydrogen-containing resin (ii)is an acrylic polyol containing an alkoxysilyl group which consistsessentially of polymerized monomers selected from the group consistingof alkyl methacrylate and an alkyl acrylate having from 1 to 12 carbonatoms in the alkyl group, hydroxy alkyl methacrylate and hydroxy alkylacrylate having from 1 to 4 carbon atoms in the alkyl group, isobornylmethacrylate, isobornyl acrylate, styrene and any mixtures thereof incombination with ethylenically unsaturated silane monomer (III), above,wherein R⁴ is methyl, ethyl, methoxy or ethoxy; each R⁵ and R⁶ areindependently methyl or ethyl; R⁷ is hydrogen or methyl; and, thesubscript n is an integer of from 0 to 2.

(2) Amine-Functional Resin (iv)

In one embodiment, amine-functional resin (iv) is represented by generalformula (VI):

[H(R⁹)N-]_(g)R¹⁰  (VI)

wherein:

R⁹ is hydrogen, a linear, cyclic or branched hydrocarbon group havingfrom 1 to 18 carbon atoms, which is optionally substituted byheteroatoms, such as an alkyl radical which is interrupted bynonadjacent oxygen atoms, an alkoxy group —OR¹¹ or an acyloxy group—O—C(═O)—R¹² wherein R¹¹ is hydrogen or a linear, cyclic or branchedhydrocarbon group having from 1 to 18 carbon atoms and R¹² is a hydrogenor a hydrocarbon contain from 1 to 18 carbon atoms;

R¹⁰ is a linear or branched polymer group having a number averagemolecular weight of from 500 to 25,000, as determined in accordance withDIN Standard 55672 (1) using polystyrene standards; and,

g is an integer greater than 1.

In one embodiment, amine-functional resin (iv) is at least one ofamino-terminated poly(alkylene oxide), amine-terminated polyurethane andamine-terminated polyamide. Suitable amine-functional resins (iv)include Desmophen NH 1420 from Bayer and Jeffamine D-2000 from Huntsman.

(3) Mercapto-Functional Resin (v)

In one embodiment, mercapto-functional resin (v) is represented bygeneral formula (VII):

R¹³SH)_(h)  (VII)

wherein:

R¹³ is a linear or branched polymer group having a number averagemolecular weight of from 500 to 25,000, as determined in accordance withDIN Standard 55672 (1) using polystyrene standards; and,

h is an integer greater than 1.

In one embodiment, mercapto-functional resin (v) is amercapto-terminated polysulfide, a mercapto-terminated poly(alkyleneoxide) or a mercapto-terminated polyurethane. Suitablemercapto-functional resins (v) include Thioplast G 44 from Akzo Nobel.

Mercapto-functional resin (v) includes thiol ester compounds having anaverage of two or more thiol groups.

The thiol ester can be a compound having an average of at least 1.5ester groups and an average of at least 1.5 thiol groups. Suitable thiolester compounds can also include one or more cyclic sulfide groups inwhich the ratio of such sulfide group(s) to thiol group(s) is less than1.5.

Generally, the thiol ester compound contains at least one ester groupand greater than one thiol group. The thiol ester compound can beproduced from any unsaturated ester. For instance, the thiol ester canbe derived from an unsaturated natural source oil or from an unsaturatedtriglyceride. In some instances, the thiol ester compound can bedescribed as a mercaptanized unsaturated ester wherein the unsaturatedester can be any unsaturated ester described herein. For instance, thethiol ester can be a mercaptanized unsaturated natural source oil or amercaptanized unsaturated triglyceride. Because the feedstockunsaturated esters can contain multiple carbon-carbon double bonds perunsaturated ester molecule, carbon-carbon double bond reactivity andstatistical probability dictate that each thiol ester molecule of thethiol ester composition produced from the unsaturated ester compositionmay not have the same number of thiol groups, number of unreactedcarbon-carbon double bonds, number of cyclic sulfides, molar ratio ofcarbon-carbon double bonds to thiol groups, molar ratio of cyclicsulfides to thiol groups, and other quantities of functional groups andmolar ratios disclosed herein as the feedstock unsaturated ester.Additionally, the feedstock unsaturated esters can also comprise amixture of individual unsaturated esters having a different number ofcarbon-carbon double bonds and/or ester groups. Thus, many of theseproperties may be stated as an average number of the groups per thiolester molecule within the thiol ester composition, or average ratio perthiol ester molecule within the thiol ester composition. In otherembodiments, it is desired to control the content of thiol sulfurpresent in the thiol ester. Because it is difficult to ensure that thehydrogen sulfide reacts with every carbon-carbon double bond within theunsaturated ester, certain molecules of thiol ester can have more orless thiol groups than other molecules. Thus, the weight percent ofthiol groups is stated as an average across all thiol ester molecules ofthe thiol ester compound(s).

The thiol ester compound can be derived from any unsaturated esterdescribed herein. The thiol ester can be described as comprising one ormore separate or discrete functional groups of the thiol estercompound(s). These independent functional groups can include: the numberof (or average number of) ester groups per thiol ester molecule, thenumber of (or average number of) thiol groups per thiol ester molecule,the number of (or average number of) unreacted carbon-carbon doublebonds per thiol ester molecule, the average thiol sulfur content of thethiol ester compound(s), the percentage (or average percentage) ofsulfide linkages per thiol ester molecule, and the percentage (oraverage percentage) of cyclic sulfide groups per thiol ester molecule.Additionally, the thiol ester compound(s) can be described usingindividual or a combination of ratios including the ratio of doublebonds to thiol groups, the ratio of cyclic sulfides to mercaptan group,and the like.

Minimally, in some embodiments, the thiol ester compound(s) have atleast one ester group and one thiol group per thiol ester molecule. Asthe thiol ester is prepared from unsaturated esters, the thiol ester cancontain the same number of ester groups as the unsaturated estersdescribed herein. In an embodiment, the thiol ester compound(s) have anaverage of at least 1.5 ester groups per thiol ester molecule.Alternatively, the thiol ester molecules have an average of at least 2ester groups per thiol ester molecule, alternatively, an average of atleast 2.5 ester groups per thiol ester molecule; or alternatively, anaverage of at least 3 ester groups per thiol ester molecule. In otherembodiments, the thiol esters have an average of from 1.5 to 8 estergroups per thiol ester molecule; alternatively, an average of from 2 to8 ester groups per thiol ester molecule; alternatively, an average offrom 2.5 to 5 ester groups per thiol ester molecule; or alternatively,an average of from 3 to 4 ester groups per thiol ester molecule. In yetother embodiments, the thiol ester comprises an average of about 3 estergroups per thiol ester molecule, or alternatively, an average of about 4ester groups per unsaturated ester molecule.

Minimally, the thiol ester comprises an average greater than one thiolgroup per thiol ester molecule. In an embodiment, the thiol estermolecules have an average of at least 1.5 thiol groups per thiol estermolecule; alternatively, an average of at least 2 thiol groups per thiolester molecule; alternatively, an average of at least 2.5 thiol groupsper thiol ester molecule; or alternatively, an average of at least 3thiol groups per thiol ester molecule. In other embodiments, the thiolester compound(s) have an average of from 1.5 to 9 thiol groups perthiol ester molecule; alternatively, an average of from 2 to 9 thiolgroups per thiol ester molecule; alternatively, an average of from 2 to6 thiol groups per thiol ester molecule, or alternatively, an average offrom 3 to 8 thiol groups per thiol ester molecule.

In some embodiments, the thiol ester compound(s) can have an average offrom 2 to 8 ester groups per thiol ester molecule, and an average offrom 2 to 9 thiol groups per thiol ester molecule; alternatively, anaverage of from 2 to 7 ester groups per thiol ester molecule, and anaverage of from 2 to 8 thiol groups per thiol ester molecule; oralternatively, an average of from 2.5 to 5 ester groups per thiol estermolecule, and an average of from 2 to 6 thiol groups per thiol estermolecule.

In a non-limiting embodiment, the thiol ester includes compounds derivedfrom unsaturated ester, e.g., at least one of unsaturated natural sourceoil, unsaturated triglyceride, mercaptanized unsaturated natural sourceoil and mercaptanized unsaturated triglyceride. In these and othernon-limiting embodiments, the thiol ester molecules can have an averageof from 2 to 8 ester groups per thiol ester molecule and an average offrom 2 to 9 thiol groups per thiol ester molecule; or alternatively, anaverage of from 2.5 to 5 ester groups per thiol ester molecule and anaverage of from 2 to 6 thiol groups per thiol ester molecule.

In other embodiments, the thiol ester compound(s) can be described bythe average amount of thiol sulfur present therein. In one embodiment,the thiol ester molecules have an average of at least 5 weight percentthiol sulfur per thiol ester molecule; alternatively, an average of atleast 10 weight percent thiol sulfur per thiol ester molecule, oralternatively, an average of greater than 15 weight percent thiol sulfurper thiol ester molecule. In another embodiment, the thiol estercompound(s) have an average of from 5 to 25 weight percent thiol sulfurper thiol ester molecule; alternatively, an average of from 5 to 20weight percent thiol sulfur per thiol ester molecule; alternatively, anaverage of from 6 to 15 weight percent thiol sulfur per thiol estermolecule; or alternatively, an average of from 8 to 10 weight percentthiol sulfur per thiol ester molecule.

Generally, the location of the thiol group of the thiol ester is notparticularly important and will be dictated by the method used toproduce the thiol ester. In embodiments wherein the thiol ester isproduced by contacting an unsaturated ester with hydrogen sulfide, theposition of the thiol group will be dictated by the position of thecarbon-carbon double bond. When the carbon-carbon double bond is aninternal carbon-carbon double bond, the method of producing the thiolester will result in a secondary thiol group. However, when the doublebond is located at a terminal position it is possible to choose reactionconditions to produce a thiol ester comprising either a primary thiolgroup or a secondary thiol group. In one embodiment, the thiol estercomposition can comprise, or consist essentially of, thiol estermolecules comprising one or more secondary thiol groups.

Some methods of producing the thiol ester compounds additionally cancreate sulfur-containing functional groups other than a thiol group. Forexample, in some thiol ester production methods, an introduced thiolgroup can react with a carbon-carbon double bond within the sameunsaturated ester to produce a sulfide linkage. When the reaction iswith a double bond of a second unsaturated ester, this produces a simplesulfide linkage. However, in some instances, the second carbon-carbondouble bond is located in the same unsaturated ester molecule. When thethiol group reacts with a second carbon-carbon double bond within thesame unsaturated ester molecule, a sulfide linkage is produced. In someinstances, the carbon-carbon double bond can be within a second estergroup of the unsaturated ester molecule. While in other instances, thecarbon-carbon double bond can be within the same ester group of theunsaturated ester molecule.

When the thiol group reacts with the carbon-carbon double bond in asecond ester group of the same unsaturated ester molecule, the resultingcyclic sulfide will contain two ester groups contained within a ringstructure. When the thiol group reacts with the carbon-carbon doublebond within the same ester group, the resulting cyclic sulfide will notcontain an ester group within the ring structure. Within thisspecification, this second type of cyclic sulfide is referred to as acyclic sulfide. Within this specification, the first type of cyclicsulfide is referred to as a simple sulfide. In the cyclic sulfide case,the sulfide linkage produces a cyclic sulfide functionality within asingle ester group of the thiol ester. This linkage is termed a cyclicsulfide for purposes of this application. One such sulfide group thatcan be produced is a cyclic sulfide. The cyclic sulfide rings that canbe produced include a tetrahydrothiopyran ring, a thietane ring, or athiophane ring (tetrahydrothiophene ring).

In some embodiments, it is desirable to control the average amount ofsulfur present as cyclic sulfide in the thiol ester. In an embodiment,the average amount of sulfur present as cyclic sulfide in the thiolester molecules comprises less than 30 mole percent. Alternatively, theaverage amount of sulfur present as cyclic sulfide in the thiol estermolecules comprises less than 20 mole percent; alternatively, less than10 mole percent; alternatively, less than 5 mole percent; oralternatively, less than 2 mole percent. In other embodiments, it isdesired to control the molar ratio of cyclic sulfide groups to thiolgroups. In an embodiment, the average molar ratio of cyclic sulfidegroups to thiol group per thiol ester molecule is less than 1.5.Alternatively, the average molar ratio of cyclic sulfide groups to thiolgroup per thiol ester molecule is less than 1; alternatively, less than0.5; alternatively, less than 0.25; or alternatively, less than 0.1. Insome embodiments, the ratio of cyclic sulfide groups to thiol group perthiol ester ranges from 0 to 1; alternatively, the average molar ratioof cyclic sulfide groups to thiol group per thiol ester molecule rangesbetween 0.05 and 1; alternatively, between 0.05 and 0.75; alternatively,between 0.05 and 0.5; or alternatively, between 0.05 and 0.25.

In some instances it can desirable to have carbon-carbon double bondspresent in the thiol ester compound(s), while in other embodiments itcan be desirable to minimize the number of carbon-carbon double bondspresent in the thiol ester compound(s). The presence of carbon-carbondouble bonds present in the thiol ester can be stated as an averagemolar ratio of carbon-carbon double bonds to thiol-sulfur. In oneembodiment, the average ratio of the remaining unreacted carbon-carbondouble bond in a thiol ester compound to thiol sulfur is less than 1.5per thiol ester molecule. Alternatively, the average ratio ofcarbon-carbon double bond to thiol sulfur is less than 1.2 per thiolester molecule; alternatively, less than 1.0 per thiol ester molecule;alternatively, less than 0.75 per thiol ester molecule; alternatively,less than 0.5 per thiol ester molecule; alternatively, less than 0.2 perthiol ester molecule; or alternatively, less than 0.1 per thiol estermolecule.

In particular embodiments, the thiol ester is produced from anunsaturated ester compound. Because the feedstock unsaturated ester hasparticular compositions having a certain number of ester groups present,the product thiol ester composition will have about the same number ofester groups per thiol ester molecule as the feedstock unsaturatedester. Other, independent thiol ester properties described herein can beused to further describe the thiol ester compound(s).

In some embodiments, the thiol ester compound(s) are produced fromunsaturated esters having an average of less than 25 weight percent ofside chains having 3 contiguous methylene interrupted carbon-carbondouble bonds, as described herein. In some embodiments, greater than 40percent of the thiol containing natural source total side chains caninclude sulfur. In some embodiments, greater than 60 percent of thethiol ester molecule total side chains can include sulfur. In otherembodiments, greater than 50, 70, or 80 percent of the thiol estermolecule total side chains can include sulfur.

The thiol ester compound(s) also can be described as product(s) obtainedby the process comprising contacting hydrogen sulfide and an unsaturatedester composition wherein the unsaturated ester can be any unsaturatedester described herein, and can be further limited by the process asdescribed herein. The thiol esters derived from an unsaturated naturalsource oil or derived from an unsaturated triglyceride also can bedescribed using a molecular weight or an average molecular weight of theside chains. Alternatively, the thiol ester compound(s) can be describedas a mercaptanized unsaturated ester, wherein the unsaturated ester canbe any unsaturated ester described herein. The thiol esters described asa mercaptanized unsaturated natural source oil or a mercaptanizedunsaturated triglyceride can also be described using a molecular weightor an average molecular weight of the side chains.

Curing Agent (vi)

The curing agent (vi) can be at least one of an isocyanate-containingcompound (vii), blocked isocyanate-containing compound (viii) andaminoplast (ix).

(1) Isocyanate-Containing Compound (vii)

The preferred curing agent (vi) is an isocyanate-containing compound(vii). In one embodiment, isocyanate-containing compound (vii) is aconventional substituted or unsubstituted aromatic, aliphatic,cycloaliphatic and/or heterocyclic polyisocyanate. Isocyanate-containingcompound (vii) can have from 2 to 5 isocyanate groups per molecule.Exemplary isocyanates are described in “Methoden der organischen Chemie”[Methods of Organic Chemistry], Houben-Weyl, volume 14/2, 4th Edition,Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken,Liebigs Ann. Chem. 562, 75 to 136.

Suitable examples of isocyanate-containing compound (vii) include1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4- and2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, omega,omega′-diisocyanatodipropyl ether, cyclobutane1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 2,2- and2,6-diisocyanato-1-methylcyclohexane,3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (“isophoronediisocyanate”), 2,5- and3,5-bis(isocyanatomethyl)-8-methyl-1,4-methano-decahydronaphthalene,1,5-, 2,5-, 1,6- and2,6-bis(isocyanatomethyl)-4,7-methanohexahydroindane, 1,5-, 2,5-, 1,6-and 2,6-bis(isocyanato)-4,7-methylhexahydroindane, dicyclohexyl2,4′- and4,4′-diisocyanate, 2,4- and 2,6-hexahydrotolylene diisocyanate, perhydro2,4′- and 4,4′-diphenylmethane diisocyanate,omega,omega′-diisocyanato-1,4-diethylbenzene, 1,3- and 1,4-phenylenediisocyanate, 4,4′-diisocyanatobiphenyl,4,4′-diisocyanato-3,3′-dichlorobiphenyl,4,4′-diisocyanato-3,3′-dimethoxybiphenyl,4,4′-diisocyanato-3,3′-dimethylbiphenyl,4,4′-diisocyanato-3,3′-diphenylbiphenyl, 2,4′- and4,4′-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, tolylenediisocyanates, such as 2,4- and 2,6-tolylene diisocyanate,N,N′-(4,4′-dimethyl-3,3′-diisocyanatodiphenyl)uretdione, m-xylylenediisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylenediisocyanate, 2,4,4′-triisocyanatodiphenyl ether and4,4′,4″-triisocyanatotriphenyl methane.

Isocyanate-containing compound (vii) can also contain one or moreisocyanurate groups, biuret groups, allophanate groups, urethane groupsand/or urea groups. Polyisocyanates containing urethane groups, forexample, are obtained by reacting some of the isocyanate groups withpolyols, for example trimethylol propane and glycerol.

Examples of preferred isocyanate-containing compounds (vii) are2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethanediisoyanate, 2,4′-diphenylmethane diisocyanate, p-phenylenediisocyanate, biphenyl diisocyanates, 3,3′-dimethyl-4,4′-diphenylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, isophoronediisocyanate, ethylene diisocyanate, 1,12-dodecane diisocyanate,1,3-cyclobutane diisocyanate, 1,3-cyclohexane diisocyanate,1,4-cyclohexane diisocyanate, methylcyclohexyl diisocyanates,2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate,1,3-hexahydrophenylene diisocyanate, 1,4-hexahydrophenylenediisocyanate, 2,4′-perhydrodiphenylmethane diisocyanate,4,4′-methylenedicyclohexyl diisocyanate (e.g., Desmodur® W from BayerAG), tetramethylxylyl diisocyanates (e.g., TMXDI® from AmericanCyanamid), and mixtures of the aforementioned polyisocyanates. Furtherpreferred isocyanate-containing compounds (vii) are the biuret dimersand the isocyanurate trimers of the aforementioned diisocyanates.Particularly preferred isocyanate-containing compounds (vii) are1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and4,4′-methylenedicyclohexyl diisocyanate, their biuret dimers and/orisocyanurate trimers.

In one preferred embodiment, isocyanate-containing compound (vii) isobtained by prereacting at least one polyisocyanate, e.g., any of thoselisted above, with a secondary aminosilane. The equivalent ratio ofisocyanate groups of the polyisocyanate reactant(s) to amino groups ofthe secondary aminosilane reactant(s) can generally range from 1.1:1.0to 50.0:1.0, preferably from 2.0:1 to 10:1 and more preferably from2.5:1.0 to 5.0:1.0. The resulting curing agent has at least oneisocyanate group, at least one hydrolyzable silyl group and at least oneureido group. Suitable secondary aminosilanes used in the preparation ofthis embodiment of isocyanate-containing compound (vii) includeN-methyl-3-aminopropyltrimethoxysilane,N-ethyl-3-aminopropyltrimethoxysilane,N-butyl-3-aminopropyltrimethoxysilane,N-ethyl-3-amino-2-methylpropyltrimethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,bis-[3-trimethoxysilylpropyl]amine,N-methyl-3-aminopropyltriethoxysilane,N-ethyl-3-aminopropyltriethoxysilane,N-butyl-3-aminopropyltriethoxysilane,N-ethyl-3-amino-2-methylpropyltriethoxysilane,N-phenyl-3-aminopropyltriethoxysilane,bis-[3-triethoxysilylpropyl]amine, etc., and their mixtures. Thus, e.g.,isocyanate-containing compound (vii) is obtained by reacting HDIisocyanurate trimer and bis-[3-trimethoxysilylpropyl]amine at 1:0.99 to1:0.01 equivalents.

(2) Blocked Isocyanate-Containing Compound (viii)

As previously indicated, curing agent (vi) can be at least one blockedisocyanate-containing compound (viii). Such compounds, as is known, canbe obtained from the reaction of a polyisocyanate with a blocking agentsuch as an alcohol, phenol, oxime, beta-ketoester, malonate ester, andthe like. Suitable polyisocyanate compounds are those described above inconnection with isocyanato-containing compound (vii). Some suitableblocking agents include methanol, ethanol, isopropy alcohol, n-propanol,n-butyl alcohol, propan-2-one oxime, butan-2-one oxime, acetoacetone,dimethyl malonate and diethyl malonate.

(3) Aminoplast (ix)

In one embodiment, aminoplast (ix) representatives of curing agent (vi)are aminoplast resin compositions derived by reacting a polyamine orpolyamide compound with an aldehyde, followed by a subsequentetherification reaction with an alcohol.

Polyamine compounds contain two or more amino groups, while polyamidecompounds contain two or more amido groups. Such compounds can includetriazines, diazines, triazoles, guanadines, guanamines, and alkyl- andaryl-substituted derivatives of these compounds, including alkyl- andaryl-substituted ureas, alkyl- and aryl-substituted melamines, and thelike, or combinations thereof. For instance, suitable polyamine orpolyamide compounds can comprise, consist essentially of, or consist of,melamine, urea, glycoluril, benzoguanamine, acetoguanamine,formoguanamine, spiroguanamine, N,N′-dimethyl urea, benzourea,dicyandiamide, ammeline, 2-chloro-4,6-diamino-1,3,5-triazine,6-methyl-2,4-diamino-1,3,5-triazine, 3,5-diaminotriazole,triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine,3,4,6-tris(ethylamino)-1,3,5 triazine, or combinations of two or more ofthese compounds.

Aminoplast (ix) can be derived from a polyamine compound. In one aspect,the polyamine compound can be a C₁-C₄₀ polyamine having at least twoamine groups, wherein the amine groups are either a primary amine group,a secondary amine group, or a combination thereof. Alternatively, thepolyamine compound can be a C₁-C₃₀ polyamine, a C₁-C₂₀ polyamine, aC₁-C₁₂ polyamine, or a C₁-C₈ polyamine. In another aspect, the polyaminecompound can have the formula (VIII):

R¹⁴(NR¹⁵H)_(m)  (VIII)

wherein R¹⁴ is a C₁-C₂₀ organyl group or a C₁-C₂₀ hydrocarbyl group, andeach occurrence of R¹⁵ is independently a hydrogen or a C₁-C₂₀hydrocarbyl group, and the subscript m is an integer of from least 2 to15. In some aspects of this invention, R¹⁴ can be a C₁-C₈ organyl groupor a C₁-C₈ hydrocarbyl group, and R¹⁵, in each occurrence, can behydrogen or a C₁-C₈ hydrocarbyl group, and m can be equal to 2 or,alternatively, m can be equal to 3. In other aspects, R² can be H ineach occurrence. The C₁-C₂₀ hydrocarbyl group or C₁-C₈ hydrocarbyl groupemployed as R¹⁴ and R¹⁵ can be any alkyl group, aryl group, or alkylarylgroup. Alkyl groups include, but are not limited to, methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, and the like. Aryl and arylalkyl groups include, but are notlimited to, phenyl, alkyl-substituted phenyl, naphthyl,alkyl-substituted naphthyl, phenyl-substituted alkyl,naphthyl-substituted alkyl, and the like.

Unless otherwise specified, the disclosure of an alkyl group is intendedto include all structural isomers, linear or branched, of a givenmoiety. Additionally, unless otherwise specified, the disclosure of analkyl group is intended to include all enantiomers and alldiastereomers. As examples, unless otherwise specified, the term propylis meant to include n-propyl and iso-propyl, the term butyl is meant toinclude n-butyl, iso-butyl, t-butyl, sec-butyl, and the term octylincludes n-octyl, 2-ethylhexyl and neooctyl, among other isomers. Unlessotherwise specified, any aryl group or arylalkyl group used hereinincludes all structural isomers (regioisomers, and linear or branchedisomers), enantiomers, and diastereomers. For example, the term tolyl ismeant to include any possible substituent position, that is,2-methylphenyl, 3-methylphenyl, and/or 4-methylphenyl, and the term theterm xylyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, and 3,6-dimethylphenyl.

In an aspect, the alkyl, aryl, and alkyl aryl groups which can beemployed as R¹⁴ and R¹⁵ independently can be methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, neo-pentyl, phenyl,benzyl, tolyl, xylyl (dimethylphenyl), trimethylphenyl, phenylethyl,phenylpropyl, phenylbutyl, propyl-2-phenylethyl, or naphthyl. In anaspect, the alkyl groups which can be employed as R¹⁴ and R¹⁵independently can be methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, t-butyl, n-pentyl, and neo-pentyl. In an aspect, the aryl oraryl alkyl groups which can be employed as R¹⁴ and R¹⁵ independently canbe phenyl, benzyl, tolyl, xylyl (dimethylphenyl), trimethylphenyl,phenylethyl, phenylpropyl, phenylbutyl, and propyl-2-phenylethyl;alternatively, phenyl; alternatively, benzyl; alternatively, tolyl; oralternatively, xylyl.

The C₁-C₂₀ organyl group or C₁-C₈ organyl group employed as R¹⁴ can beany functional group described herein that contains an atom other thanhydrogen and carbon. For instance, the organyl group can comprise,consist essentially of, or consist of, a diazine, a triazine, or atriazole, any of which can be substituted with an alkyl group, arylgroup, or alkylaryl group. Hence, R¹⁵ can comprise, consist essentiallyof, or consist of, 1,3,5-triazine in one aspect of this invention, andin another aspect, R¹⁴ can comprise, consist essentially of, or consistof, 2-phenyl-1,3,5-triazine.

Yet, in other aspects of this invention, the polyamine compound cancomprise, consist essentially of, or consist of, melamine, guanamine, asubstituted guanamine, or any combination thereof. For instance, thepolyamine compound can comprise, consist essentially of, or consist of,melamine; alternatively, guanamine; or alternatively, a substitutedguanamine, such as benzoguanamine. Moreover, the polyamine compound cancomprise, consist essentially of, or consist of, a diazine, a triazine,or a triazole moiety in some aspects of this invention.

Aminoplast (ix) can be derived from a polyamide compound. In one aspect,the polyamide compound can be a C₁-C₄₀ polyamide having at least twoamide groups, wherein at least one hydrogen atom is attached to eachamide nitrogen atom. Hence, the amide nitrogen can have one hydrogenatom or two hydrogen atoms. In another aspect, the polyamide compoundcan be a C₁-C₃₀ polyamide, a C₁-C₂₀ polyamide, a C₁-C₁₂ polyamide, or aC₁-C₈ polyamide. In yet another aspect, the polyamide compound can haveeither the formula (IX) or (X):

CO(NR¹⁵H)₂  (IX); or

R¹⁴(cO)(NR¹⁵H)_(m)  (X)

wherein R¹⁴ can be a C₁-C₂₀ organyl group or a C₁-C₂₀ hydrocarbyl group,and R¹⁵, in each occurrence, can be hydrogen or a C₁-C₂₀ hydrocarbylgroup, and m is at least 2. In some aspects, R¹⁴ can be a C₁-C₈ organylgroup or a C₁-C₈ hydrocarbyl group, and R¹⁵, in each occurrence, can behydrogen or a C₁-C₈ hydrocarbyl group, and m can be equal to 2 or,alternatively, m can be equal to 3. In other aspects, R¹⁴ can behydrogen in each occurrence.

Suitable organyl and hydrocarbyl selections for R¹⁴ and hydrocarbylselections for R¹⁵ for the polyamide compound can be as described abovefor the polyamine compound. For instance, representative alkyl, aryl,and alkyl aryl selections for R¹⁴ and R¹⁵ independently can be methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl,neo-pentyl, phenyl, benzyl, tolyl, xylyl (dimethylphenyl),trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, or naphthyl.

Yet, in other aspects disclosed herein, the polyamide compound cancomprise, consist essentially of, or consist of, urea, glycoluril, or acombination thereof. For instance, the polyamide compound can comprise,consist essentially of, or consist of, urea; or alternatively,glycoluril.

In the preparation of aminoplast resin compositions, the first stepgenerally is the reaction of a polyamine or polyamide compound with analdehyde. This reaction is often referred to as an alkylolation (or amethylolation, in the case of formaldehyde). A single aldehyde, or amixture or combination of two or more aldehydes, can be used in thisreaction. In one aspect of the present invention, the aldehyde can be aC₁-C₁₈ aldehyde. In another aspect, the aldehyde can be C₁-C₁₀ aldehyde.For instance, the aldehyde can comprise, consist essentially of, orconsist of, formaldehyde, acetaldehyde, propionaldehyde,n-butyraldehyde, isobutyraldehyde, valeraldehyde, hexanaldehyde,octylaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural,glyoxal, glutaraldehyde, and the like, or combinations thereof. In yetanother aspect, the aldehyde can comprise, consist essentially of, orconsist of, formaldehyde; alternatively, acetaldehyde; or alternatively,benzaldehyde.

Depending upon the ratio of polyamine/polyamide to aldehyde, mixtures ofpartially alkylolated derivatives can result. The molar ratio ofamino/amido groups (e.g., primary and secondary) in thepolyamine/polyamide compound to aldehyde groups in the aldehydetypically falls within a range from 1:10 to 50:1, from 1:2 to 25:1, orfrom 1:1 to 10:1. Alkylolated derivatives, which can be used tosynthesize aminopiast (ix), can have the formula (XI):

R¹⁴(NR¹⁶R¹⁷)_(m)  (XI)

wherein R¹⁴ is a C₁-C₂₀ organyl group or a C₁-C₂₀ hydrocarbyl group, andeach occurrence of R¹⁶ and R¹⁷ is independently —H, —CH₂OH, or —CH₂OR¹⁴,and m is at least 2. For instance, m can be equal to 2 or,alternatively, n can be equal to 3. In each occurrence, R¹⁶ can be aC₁-C₁₀ hydrocarbyl group. Alternatively, in each occurrence, R¹⁶ can bea C₁-C₈ hydrocarbyl group; alternatively, a C₁-C₆ hydrocarbyl group;alternatively, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, oriso-butyl; or alternatively, methyl or butyl. In some aspects of thisinvention, R¹⁴ can be a C₁-C₁₂ organyl group or a C₁-C₁₂ hydrocarbylgroup, while in other aspects, R¹⁴ can be a C₁-C₈ organyl group or aC₁-C₈ hydrocarbyl group.

In the preparation of aminoplast resin compositions, the second stepgenerally is an etherification reaction with an alcohol. This reaction,based on the ratio of the alkylolated reaction product to the alcoholcan result in complete or partial etherification. Oligomericspecies—dimers, trimers, higher oligomers, and so forth—also can resultfrom the preparation of an aminoplast resin composition, and sucholigomeric products are also encompassed herein. Often, the alcoholemployed is a monohydric alcohol. Suitable alcohols can include, but arenot limited to, methanol, ethanol, propanol, isopropanol, n-butanol,isobutanol, pentanol, hexanol, heptanol, octanol, and the like, as wellas benzyl alcohol, phenol, and other aromatic alcohols, cyclic alcoholssuch as cyclohexanol, monoethers of glycols, and halogen-substituted orother substituted alcohols, such as 3-chloropropanol and butoxyethanol.More than one alcohol can be used and, therefore, mixtures orcombinations of alcohols are contemplated. For instance, mixtures ofmethanol/n-butanol, methanol/isobutanol, methanol/ethanol,methanol/isooctanol, and the like, can be employed. Any ratio of therespective alcohols can be used, but typically, the molar ratio is in arange of 10:1 to 1:10, for example, from 6:1 to 1:6, or from 3:1 to 1:3.

In the present invention, the alcohol used in the preparation of theaminoplast (ix) can comprise (or consist essentially of, or consist of)methanol. In another aspect, the alcohol can comprise (or consistessentially of, or consist of) ethanol. In still another aspect, thealcohol can comprise (or consist essentially of or consist of) butanol(e.g., n-butanol, isobutanol, etc.). In yet another aspect, the alcoholcan comprise (or consist essentially of, or consist of) benzyl alcohol.

In one embodiment of this invention, aminoplast (ix) can comprise,consist essentially of, or consist of, molecules having the formula(XII)-(XIV):

wherein each occurrence of R²¹, R²², R²³, R³², R³³, R³⁴, R³⁵, R⁴¹, R⁴²,R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ is independently —H, —CH₂OH, or CH₂OR¹⁴, whereineach occurrence of R¹⁸ is a C₁-C₁₀ hydrocarbyl group, and R³¹ is amethyl group or a phenyl group. In some aspects, the alkyl, aryl, andalkyl aryl groups which can be employed as R¹⁸ independently can bemethyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-pentyl,neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl hexyl, phenyl, benzyl,tolyl, xylyl (dimethylphenyl), trimethylphenyl, phenylethyl,phenylpropyl, naphthyl, and the like. In some aspects of this invention,R²¹, R²² and R²³ independently can be —H, —CH₂OH, or CH₂OR¹⁸, whereineach occurrence of R¹⁸ is independently methyl, ethyl, n-propyl,iso-propyl, n-butyl, t-butyl, or iso-butyl. In other aspects of thisinvention, R³¹ can be a methyl group or a phenyl group, and eachoccurrence of R³², R³³, R³⁴ and R³⁵ is independently —H, —CH₂OH, or—CH₂OR¹⁸, wherein each occurrence of R¹⁸ is C₁-C₁₀ hydrocarbyl group;alternatively, a C₁-C₈ hydrocarbyl group; alternatively, a C₁-C₆hydrocarbyl group; alternatively, methyl, ethyl, n-propyl, iso-propyl,n-butyl, t-butyl, or iso-butyl; or alternatively, methyl or butyl.Furthermore, in other aspects, each occurrence of R⁴¹, R⁴², R⁴³, R⁴⁴,R⁴⁵, and R⁴⁶ is independently —H, —CH₂OH, or —CH₂OR¹⁸, wherein eachoccurrence of R¹⁸ is independently a C₁-C₁₀ hydrocarbyl group;alternatively, a C₁-C₈ hydrocarbyl group; alternatively, a C₁-C₆hydrocarbyl group; alternatively, methyl, ethyl, n-propyl, iso-propyl,n-butyl, t-butyl, or iso-butyl; or alternatively, methyl or butyl.

In these formulas, R²¹, R²², R²³, R³², R³³, R³⁴, R³⁵, R⁴¹, R⁴², R⁴³,R⁴⁴, R⁴⁵, and R⁴⁶ independently can be —H, —CH₂OH, or CH₂OR¹⁸, whereinR¹⁸, in each occurrence, can be a C₁-C₁₀ hydrocarbyl group, and R³¹ canbe a methyl group or a phenyl group. In some aspects, the alkyl, aryl,and alkyl aryl groups which can be employed as R¹⁸ independently can bemethyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-pentyl,neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl hexyl, phenyl, benzyl,tolyl, xylyl (dimethylphenyl), trimethylphenyl, phenylethyl,phenylpropyl, naphthyl, and the like. For instance, R¹⁸, in eachoccurrence, can be methyl, ethyl, n-propyl, iso-propyl, n-butyl,t-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, or 2-ethylhexyl; alternatively, R¹⁸, in each occurrence, can be phenyl, benzyl,tolyl, xylyl (dimethyiphenyl), trimethylphenyl, phenylethyl,phenylpropyl, or naphthyl; alternatively, R¹⁸, in each occurrence, canbe methyl, ethyl, n-propyl, iso-propyl, n-butyl, or t-butyl;alternatively, R¹⁸, in each occurrence, can be methyl or n-butyl; oralternatively, R¹⁸, in each occurrence, can be phenyl, benzyl, tolyl, orxylyl. In some aspects of this invention, R²¹, R²², R²³ and R²⁴independently can be —H, —CH₂OH, or —CH₂OR¹⁸, wherein R¹⁸, in eachoccurrence, can be a C₁-C₁₀ hydrocarbyl group; alternatively, a C₁-C₈hydrocarbyl group; alternatively, a C₁-C₆ hydrocarbyl group;alternatively, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, oriso-butyl; or alternatively, methyl or butyl. In other aspects of thisinvention, R³¹ can be a methyl group or a phenyl group, and R³², R³³,R³⁴ and R³⁵ independently can be —H, —CH₂OH, or CH₂OR¹⁸, wherein R¹⁸, ineach occurrence, can be a C₁-C₁₀ hydrocarbyl group; alternatively, aC₁-C₈ hydrocarbyl group; alternatively, a C₁-C₆ hydrocarbyl group;alternatively, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, oriso-butyl; or alternatively, methyl or butyl. Furthermore, in otheraspects, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ independently can be —H,—CH₂OH, or —CH₂OR¹⁸, wherein R¹⁸, in each occurrence, can be a C₁-C₁₀hydrocarbyl group; alternatively, a C₁-C₈ hydrocarbyl group;alternatively, a C₁-C₆ hydrocarbyl group; alternatively, methyl, ethyl,n-propyl, iso-propyl, n-butyl, t-butyl, or iso-butyl; or alternatively,methyl or butyl.

In accordance with another aspect of this invention, aminoplast (ix) cancomprise molecules having the formulae (XV) or (XVI):

In these formulas, each occurrence of R²⁵, R²⁶, R²⁷, R²⁸, R³⁶, R³⁷, R³⁸,and R³⁹ is independently —H, —CH₂OH, or —CH₂OR¹⁸, wherein eachoccurrence of R¹⁸ is be a C₁-C₁₀ hydrocarbyl group. In some aspects ofthis invention, R²⁵, R²⁶, R²⁷ and R²⁸ independently can be —H, —CH₂OH,or —CH₂OR¹⁸, wherein each occurrence of R¹⁸ is independently a C₁-C₈hydrocarbyl group; alternatively, a C₁-C₆ hydrocarbyl group;alternatively, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, oriso-butyl; or alternatively, methyl or butyl. In other aspects of thisinvention, each occurrence of R³⁶, R³⁷, R³⁸ and R³⁹ is independently —H,—CH₂OH, or —CH₂OR¹⁸, wherein each occurrence of R¹⁸ is independently aC₁-C₈ hydrocarbyl group; alternatively, a C₁-C₆ hydrocarbyl group;alternatively, methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, oriso-butyl; or alternatively, methyl or butyl.

Representative aminoplast (ix) that can be employed in the presentinvention include those materials commercially available under theRESIMENE®, CYMEL®, Luwipal®, and Plastopal® tradenames. Specificnon-limiting examples include RESIMENE® 747 (methylatedmelamine-formaldehyde resin) and 755 (methylated-butylatedmelamine-formaldehyde resin); and CYMEL® 1123 (methylated-ethylatedbenzoguanamine-formaldehyde resin), 1170 (butylatedglycoluril-formaldehyde resin), U-60 (methylated urea-formaldehyderesin), and U-80 (butylated urea-formaldehyde resin). Aminoplast (ix) ofthis invention can comprise, for instance, partially methylatedmelamines, partially butylated melamines, hexaethoxymethylmelamine,hexamethoxymethylmelamine, dimethoxytetraethoxymethylmelamine,dibutoxytetramethoxymethylmelamine, butylated benzoguanamine, partiallymethylated urea, fully methylated urea, fully butylated urea,hexabutoxymethylmelamine, tetrabutoxymethylglycoluril,dimethoxymethyldiethoxymethylglycoluril, and mixtures thereof.

Curing agent (vi) is generally used in amount of from 0.5 to 5equivalents, based upon the active hydrogen content of activehydrogen-containing resin (ii), more specifically of from 1.0 to 3equivalent and even more specifically of from 1.1 to 1.6 equivalents.The active hydrogen contain can be determined from the OH number on thepolyols (iii), the N—H contain of the amine-functional resin (iv), orthe SH number on the mercapto-functional resin (v).

Flexibilizer-Reactive Component (x)

In one embodiment, flexibilizer-reactive component (x) is at least onemember selected from the group consisting of filler, resin containingsilanol-reacting group and resin containing alkoxy-reacting group.

In one embodiment, the filler is at least one member selected from thegroup consisting of particulate metal, fumed metal oxide, precipitatedmetal oxide, precipitated and ground metal carbonate and carbon black,metal sulfate, metal phosphate, silicate, and having a concentration inthe range of from 0 to 50 weight percent based on the total weight ofcomposition.

The use of any and all examples, or exemplary language provided herein,for example, “such as,” is intended merely to better illuminate thepresent teachings and does not pose a limitation on the scope of theinvention unless claimed. No language in the specification should beconstrued as indicating any non-claimed element as essential to thepractice of the present teachings.

Optional Components (xi)

Optional components can be incorporated in the compositions of theinvention in known and conventional amounts. Optional components (xi)include catalysts, organic and inorganic compounds that contribute tothe processing, flexibility and/or curing of the compositions and/ortheir cured properties. Optional components include catalyst, organicsolvent, polysiloxane resin other than Formula (I), isocyanate-reactivescavenging agent, water scavenger agent, desiccant, non-silicon-basedepoxy hardener, surfactant, colorant, rheology modifier, plasticizer,extender, filler, reinforcing agent, adhesion promoter, organic resinmodifier, UV stabilizer, wetting agent, flow and leveling additive,thixotrope, defoamer, and the like. Several of the optional componentsare more fully described below.

(1) Catalyst

Catalysts include metal-containing and non-metal-containing catalysts.Examples of catalyst include tin, titanium, zirconium, lead, ironcobalt, antimony, manganese, bismuth and zinc compounds. Other suitablenon-limiting examples of catalyst are well known in the art and includechelates of various metals such as those which can be obtained fromacetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate,acetylacetoneimine, bis-acetylaceone-alkylenediimines,salicylaldehydeimine, and the like, with the various metals such as Al,Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, andmetal oxide ions as MoO²⁺⁺, UO²⁺⁺ and the like; alcoholates andphenolates of various metals such as Ti(OR⁴⁷)₄, Sn(OR⁴⁷)₄, Sn(OR⁴⁷)₂,Al(OR⁴⁷)₃, Bi(OR⁴⁷)₃ and the like, wherein R⁴⁷ is alkyl or aryl group offrom 1 to 18 carbon atoms, and reaction products of alcoholates ofvarious metals with carboxylic acids, beta-diketones, and2-(N,N-dialkylamino)alkanols, such as well known chelates of titanium.

Additional useful catalysts include organometallic derivatives oftetravalent tin, trivalent and pentavalent As, Sb, and Bi, and metalcarbonyls of iron and cobalt; and combinations thereof. In one specificembodiment organotin compounds that are dialkyltin salts of carboxylicacids, can include the non-limiting examples of dibutyltin diacetate,dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate,dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate),dibutyltindilaurylmercaptide, dibutyltin-bis(6-methylaminocaproate), andthe like, and combinations thereof. Similarly, in another specificembodiment there may be used trialkyltin hydroxide, dialkyltin oxide,dialkyltin dialkoxide, or dialkyltin dichloride and combinationsthereof. Non-limiting examples of these compounds include trimethyltinhydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltinoxide, dioctyltin oxide, dilauryltin oxide,dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate),dibutyltin dichloride, dioctyltin dichloride, and the like, andcombinations thereof.

The amount of catalyst that generally employed in the compositions canbe from 0.0011 to 10 parts by weight per one hundred parts of activehydrogen-containing resin (ii), and more specifically, from 0.1 to 0.15parts by weight per one hundred parts of active hydrogen-containingresin (ii).

(2) Solvent

Organic solvents are used to lower the viscosity and improve the flowproperties of the uncured composition, which are especially useful whenthe composition is used as a coating. A variety of solvents may bementioned as exemplary, for example, alcohols, glycols, triols, polyols,glycol ethers, esters, ketones, hydrocarbon, and the like.

Representative and non-limiting examples of specific solvents includemono-alcohols, such as methanol, ethanol, 1-propanol, 2-propanol(i-propanol), 2-methyl-1-propanol (i-butanol), 2-methyl-2-propanol(tert-butanol), 1-butanol, 2-butanol, 2-methyl-1 butanol,2-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-pentanol, 2-pentanol,4-methyl-2-pentanol; glycols such are propylene glycol, 1,3-butanediol,1,4-butane diol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol(hexylene glycol), diethylene glycol, triethylene glycol, tetraethyleneglycol, poly(ethylene glycol), dipropylene glycol, tripropylene glycol,poly(propylene glycol), 1,5-pentanediol, esterdiol 204,2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, glycerol, glycerolethoxylate, glycerol ethoxylate-co-propoxylate triol, glycerolpropoxylate, pentaerythritol; glycol ethers such as 1-methoxy-2-propanol(propylene glycol methyl ether), 1-ethoxy-2-propanol,1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methoxyethanol,2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol,2-(2-methoxyethoxyl)ethanol, 2-(2-ethoxyethoxy)ethanol,2-(2-propoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol (butyl carbitol),di(propylene glycol) butyl ether, tri(ethylene glycol) monomethyl ether,tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutylether, poly(ethylene glycol) methyl ether, poly(ethylene glycol)dimethylether, poly(ethylene glycol-co-propylene glycol), poly(ethyleneglycol-co-propylene glycol) monobutyl ether, poly(propylene glycol)monobutyl ether, di(propylene glycol) dimethylether; esters includingmethyl acetate, ethyl acetate, ethyl lactate, 2-methoxyethyl acetate,2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-(2-methoxyethoxy)ethylacetate, 2-(2-ethoxyethoxy)ethyl acetate, 2-(2-butoxyethoxy)ethylacetate, glycol diacetate, triethylene glycol diacetate, propyleneglycol methyl ether acetate (1-methoxy-2-propanol acetate), propyleneglycol ethyl ether acetate, ketones including acetone, methyl ethylketone, 2,4-pentane dione, diacetone alcohol and hydrocarbons includingtoluene, xylene, naptha, mineral spirits, hexane, heptane, cyclohexaneand mixtures thereof.

In certain embodiments, the solvent can be present in the composition ofthe invention in an amount ranging from 1 to 80 percent by weight,advantageously from 10 to 30 percent by weight, and in some embodiments,from 10 to 25 percent by weight, based on the total weight of thecomposition.

(3) Surfactant

Surfactants may be used to aid in the wetting and leveling of thecomposition of the invention especially where the composition is used asa coating. Useful surfactants include nonionic, cationic, anionic,amphoteric and/or zwitterionic surfactants. The surfactants aretypically hydrocarbon-based, silicone-based or fluorocarbon-based.Useful surfactants having short chain hydrophobes are described in U.S.Pat. No. 5,558,806 the entire contents of which are incorporated byreference herein. Other useful surfactants include alkoxylates,especially ethoxylates, containing block copolymers including copolymersof ethylene oxide, propylene oxide, butylene oxide, and mixturesthereof; alkylarylalkoxylates, especially ethoxylates or propoxylatesand their derivatives including alkyl phenol ethoxylate;arylarylalkoxylates, especially ethoxylates or propoxylates, and theirderivatives; amine alkoxylates, especially amine ethoxylates; fatty acidalkoxylates; fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzeneand alkyl naphthalene sulfonates; sulfated fatty alcohols, amines oracid amides; acid esters of sodium isethionate; esters of sodiumsulfosuccinate; sulfated or sulfonated fatty acid esters; petroleumsulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylatedamines; and mixtures thereof.

Representative, non-limiting examples of surfactants include alkylacetylenic diols sold by Air Products under the trade name SURFONYL®,pyrrilodone-based surfactants sold by ISP under the trade nameSURFADONE-LP® 100, 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylatessold by Rhodia under the trade name RHODASURF® DA 530, ethylene diaminealkoxylates sold by BASF under the trade name TETRONICS®, ethyleneoxide/propylene oxide copolymers sold by BASF under the trade namePLURONICS®, and diphenyl ether Gemini type surfactants sold by DowChemical Corporation under the trade name DOWFAX®.

In general, the compositions herein can contain the optionalsurfactant(s) in an amount of from 0.01 to 5 weight percent,advantageously from 0.05 to 2 weight percent and in certain embodiments,from 0.1 to 1 weight percent based on the total weight of thecomposition.

(4) Colorant

The composition of the invention can include a colorant. As used herein,the term “colorant” means any substance that imparts color and/or otheropacity and/or other visual effect to the composition. The colorant canbe added to the composition in any suitable form such as discreteparticles, dispersions, solutions, flakes, etc. A single colorant or amixture of two or more colorants can be used in the composition of theinvention.

Useful colorants include pigments, dyes and tints such as those used inthe paint industry and/or listed in the Dry Color ManufacturersAssociation (DCMA), as well as special-effect materials. A useful typeof colorant can be a finely divided solid powder that is insoluble butwettable under the conditions of use. A colorant can be organic orinorganic and can be agglomerated or non-agglomerated. Colorants can beincorporated into the compositions by use of a grinding vehicle such asan acrylic grinding vehicle the use of which is familiar to thoseskilled in the art.

Illustrative useful pigments and pigment compositions include, but arenot limited to, carbazole dioxazine crude pigment, azo dyes, naphtholAS, benzimidazolone, metal complexes, isoindolinone, isoindoline andpolycyclic phthalocyanine, quinacridone, perylene, perinone,diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone,anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine,triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red(“DPPBO red”), titanium dioxide, carbon black and mixtures thereof. Theterms “pigment” and “colored filler” can be used interchangeably.

Useful dyes include, but are not limited to, those that are solventand/or aqueous based such as phthalo green or blue, iron oxide, bismuthvanadate, anthraquinone, perylene, aluminum and quinacridone.

Useful tints include, but are not limited to, pigments dispersed inwater-based or water miscible carriers such as AQUA-CHEM® 896commercially available from Degussa, Inc., CHARISMA COLORANTS® andMAXITONER INDUSTRIAL COLOR ANTS® commercially available from AccurateDispersions division of Eastman Chemical, Inc.

In general, the colorant can be present in the composition in any amountthat is sufficient to impart the desired visual and/or color effect. Thecolorant can comprise from, for example, 1 to 65 weight percent of thecomposition, such as from 3 to 40 weight percent or 5 to 35 weightpercent thereof based on the total weight of the composition.

(5) Filler

The composition of the invention can include a filler. The filler of thecomposition can be any inorganic or organic filler that reinforcesand/or extends the composition. Useful fillers include, for example,reinforcing fillers such as carbon black, fumed silica, precipitatedsilica, clays, talc, aluminum silicates, particulate metal, metalsulfates, metal phosphates, silicates, metal oxides and hydroxides, andextending fillers such as treated and untreated calcium carbonates, andthe like. Fillers can be in the form of powders, particulates,aggregates, agglomerates, platelets, fibers, etc. In one embodiment, oneor more fillers are combined with silane coupling agents.

To further improve the physical strength of the cured compositionsherein, reinforcing carbon black can be used as a main filler resultingin a black or darkly colored composition. Several commercial grades ofcarbon black useful in this invention are commercially available such asthe Corax® products from Degussa. To obtain colorless translucentcompositions, higher levels of fumed silica or precipitated silica canbe used as the main filler to the exclusion of carbon black. The surfacearea of the filler can be more than 20 m²/g.

Treated calcium carbonates having particle sizes from 0.07 microns to 4microns are preferred fillers and are available under several tradenames, such as: “Ultra Pflex®” and “Hi Pflex®” from Specialty Minerals;“Winnofil® SPM” and “Winnofil® SPT” from Zeneca Resins; “Hubercarb® 1Qt”, “Hubercarb® 3Qt” and “Hubercarb® W” from Huber and “Kotomite®” fromECC. These fillers can be used either alone or in combination.

The optional fillers can be incorporated in the composition in an amountof up to 80 weight percent, advantageously in an amount of up to 50weight percent, and in certain embodiments, in an amount of from 20weight percent to 50 weight percent based on the total weight of thecomposition.

(6) Plasticizer

The compositions herein can optionally include plasticizers. Exemplaryplasticizers include phthalates, dipropylene and diethylene glycoldibenzoates and mixtures thereof, epoxidized soybean oil, and the like.Useful commercial dioctyl and diisodecyl phthalates include “Jayflex®DOP” and “Jayflex® DIDP” from Exxon Chemical. Dibenzoate plasticizersare available as “Benzoflex® 9-88”, “Benzoflex® 50” and “Benzoflex® 400”from Velsicol Chemical Corporation. The optional plasticizer canrepresent up to 100 parts by weight per hundred parts ofioscyanate-reactive resin (i) with up to 40 parts by weight per hundredbeing preferred.

(7) Thixotrope

Useful optional thixotropes include various castor waxes, fumed silica,treated clays and polyamides. Commercially available thixotropesinclude, for example, Aerosil from Degussa, Cabo-Sil TS 720 from Cabot,Castorwax from CasChem, Thixatrol and Thixcin from Rheox, Crayvallacfrom Crayvalley Corp. and Dislon from King Industries.

(8) Isocyanate-Reactive Scavenging Agent

The optional isocyanate-reactive scavenging agent is an agent possessingat least one active hydrogen and that reacts with isocyanate at a rategreater than that of undesired reactions that cause an increase inviscosity such as the further reaction of isocyanate withhydroxyl-terminated polymers (if there is still hydroxyl present),reaction of isocyanate with urethane to form allophanate, reaction ofisocyanate with urea to form biuret and reaction of thehydroxyl-terminated polymers with an alkoxysilyl group.

The isocyanate-reactive scavenging agent can be added to the reactionmixture of isocyanate-containing compound (vii), hydroxyl-terminatedpolymer and optionally other ingredients, such as catalysts andnon-protic solvents, at a desired point at or near the end of thesilylation reaction. It is understood that for di- orpolyisocyanate-extended polyols the hydroxyl-terminated polymer maycontain residual isocyanate, either from partially reacted di- orpolyisocyanate, or from unreacted di- or polyisocyanate. The residualisocyanate present in the silylated polyurethane resin can come from thedi- or polyisocyanate used to chain extend the polyol, or from theisocyanatosilane used to react with the hydroxyl-terminated polymer. Thedesired point for the addition of the isocyanate-reactive agent can bedetermined by the viscosity of the reaction mixture, or by some othermethod. Thus, the isocyanate-reactive scavenging agent is added to thereaction mixture at a particular viscosity depending on formulation andthe desired properties of the final product. In one embodiment of theinvention, the isocyanate-reactive scavenging agent is added to thereaction mixture at a viscosity range from 1,000 cP to 150,000 cP(measured at a temperature of 25° C.), and in another embodiment of theinvention from 30,000 cP to 75,000 cP (measured at a temperature of 25°C.). In this manner, the isocyanate-reactive scavenging agent minimizesbatch-to-batch variation of the final viscosity of the silylatedpolyurethane resin.

The isocyanate-reactive scavenging agent is allowed to react with theisocyanate-containing reaction mixture for sufficient time to ensurethat all of the residual isocyanate has reacted. The isocyanate-reactivescavenging agent can be added in a stoichiometric amount relative to theresidual isocyanate, but it is preferable to add an excess of theisocyanate-reactive scavenging agent to ensure that all of the residualisocyanate is reacted and to inhibit the reaction of the residualhydroxyl groups of the hydroxyl-terminated polymer with the alkoxysilylgroups. In one embodiment of the invention, the amount ofisocyanate-reactive scavenging agent added to the isocyanate-containingreaction mixture is from 0.01 to 5 weight percent based upon the weightof active hydrogen-containing resin (ii), and from 0.01 to 0.5 weightpercent based upon the weight of active hydrogen-containing resin (ii)in another embodiment of the invention, and in still another embodimentfrom 0.02 to 0.2 weight percent based upon the weight of activehydrogen-containing resin (ii).

According to one embodiment of the invention, active hydrogen-containingresin (ii) is mixed with the isocyanate-containing compound (vii)containing less than 60 weight percent isocyanate (measured as % NCO),and in another embodiment of the invention reaction mixture of activehydrogen-containing resin (ii) and isocyanate-containing compound (vii)is further reacted with the isocyanate-reactive scavenging agent toreduced isocyanate content to less than 3 weight percent isocyanate(measured as % NCO), more specifically less than 0.5 weight percentisocyanate, and even more specifically, less than 0.01 weight percentisocyanate.

The isocyanate-reactive scavenging agent can be added neat or as amixture with one or more other materials. The disappearance of theisocyanate can be determined directly by analytical techniques such asinfra-red spectroscopy and titration, or indirectly by the measurementof constant viscosity of the reaction mixture. The synthesis can bemonitored using titration (ASTM 2572-87) or infrared analysis.

According to one embodiment of the invention, the isocyanate-scavengingagent is a mono-alcohol or a mixture of different mono-alcohols,secondary amine or mercaptan.

Mono-alcohols are generally preferred in that they have low odor, do notcontribute to the color of the silylated polyurethane resin and inhibitthe reaction of residual hydroxyl-terminated polymer with alkoxysilylgroups. Other active hydrogen compounds such as amines and organic acidstypically have strong odors, can impact color and can catalyze thereaction of the residual hydroxyl-terminated polymer with alkoxysilylgroups.

In one embodiment of the invention, the selected isocyanate-reactivescavenging agent is one that has little or no effect on the physical orcure properties of the resin or on the properties of a cured material,for example, coating, sealant, adhesive, etc., made from thecomposition.

The monoalkanol isocyanate-reactive scavenging agent possesses thegeneral formula: R⁴⁸—OH in which R⁴⁸ is a monovalent hydrocarbon groupcontaining from 1 to 30 carbon atoms and optionally may contain aheteroatom. The heteroatom can, for example, be oxygen, which can formorganofunctional groups, such as ethers, ester, and ketone groups. Inanother embodiment, the hydrocarbon group is selected from the groupconsisting of linear, branched and cyclic alkyl, and alkenyl, aryl,arenyl and aralkyl.

Representative non-limiting examples of R⁴⁸ include alkyl, such asmethyl, ethyl, propyl, isopropyl, butyl, pentyl, dodecyl, cyclohexyl,cyclopentyl, and 3-methylhexyl; alkenyl, such as vinyl, allyl andmethallyl; aryl, such as phenyl; arenyl, such as 4-methylphenyl,2,4-dimethylphenyl and 2,4,6-trimethylphenyl; and aralkyl, such asbenzyl and 2-phenylethyl.

In another embodiment of the invention, the mono-alcohols have thehydroxyl group attached to a primary carbon. A primary carbon is one inwhich at least two hydrogen atoms are attached to the carbon, —CH₂OH.The mono-alcohol scavenging agents of the invention are more reactivewith the isocyanate group because they are less sterically hindered.

According to one embodiment of the invention, useful mono-alcohols asisocyanate-reactive scavenging agents include methanol, ethanol,n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, hexanol,cyclohexanol and the like, and mixtures thereof

In a specific embodiment of the invention, when the terminal alkoxysilylgroup of active hydrogen-containing resin (ii) is a methoxysilyl, thespecific isocyanate-reactive scavenging agent is methanol. In anotherspecific embodiment of the invention, when the terminal alkoxysilylgroup of active hydrogen-containing resin (ii) is an ethoxysilyl, thespecific isocyanate-reactive scavenging agent is ethanol.

In one embodiment of the invention, the reaction mixture of activehydrogen-containing resin (ii) and isocyanate-containing compound (vii)has a reduced isocyanate content resulting from the addition ofisocyanate-scavenging agent as disclosed herein, following aging,exhibits a viscosity of 1,000 cP to 150,000 cP, more specifically from30,000 cP to 75,000 cP and most specifically from 35,000 cP to 65,000cP.

(9) Antioxidant

Optional antioxidants that can be added to the composition of theinvention to provide protection against oxidative change. The quantitiesin which antioxidants can be used vary within wide limits, for example,from 0.01 to 10 percent by weight and, more particularly, from 0.01 to 3percent by weight, based on the weight of active hydrogen-containingresin (ii).

(10) Adhesion Promoter

The composition of the invention can optionally include an adhesionpromoter. Thus, for example, the adhesion promoter can be a compound ofthe general formula (XVII):

wherein each occurrence of R⁴⁹ is independently methyl, ethyl, propyl,isopropyl, q is 0, 1 or 2 and p is 2 to 6, preferably 3.

Preferred, non-limiting examples of adhesion promoters includetrimethoxy-(3-oxiranylmethoxy-propyl)-silane anddimethoxy-methyl-(3-oxiranylmethoxy-propyl)-silane.

(11) Water Scavenger Agent

Water scavenger agent can optionally be added to the composition hereinto improve its package stability and to prevent premature curing. Itwill be understood herein that any known or commercially used waterscavenger agent can be employed herein. One type of water scavengeragent can be an alkoxysilane, for example, vinyltrimethoxysilane,methyltrimethoxysilane, and the like. The concentration of waterscavenger agent can be in the range of from 0 to 5 percent by weightbased on the weight of active hydrogen-containing resin (ii).

In an alternative to or in addition to optional water scavenging agent,desiccant can optionally be added to the composition herein to improveits package stability and to prevent premature curing. Any known orconventional desiccant, for example, silica gel, can be employed hereinfor such purposes.

As will be appreciated from the foregoing disclosure, the compositionsof the invention can be prepared by combining flexibilizer (i) ofFormula OD, active hydrogen-containing resin (ii), and curing agent(vi), as well as one or more of the previously described optionalcomponents, among others. The combination can be achieved by the use ofstatic mixers or mechanical mixers.

When used as a coating, the composition of this invention can be appliedto a desired substrate surface to protect it from weathering, impact,and exposure to corrosion and/or chemicals. Illustrative of substratesthat can be treated using compositions of this invention include wood,plastic, concrete, vitreous surfaces, and metallic surfaces. The coatingcompositions of this invention are useful, for example, as a top coatingdisposed either directly onto the substrate surface itself or disposedonto a prior or other underlying coating, as for example, an inorganicor organic primer material, disposed on the substrate surface to achievea desired purpose.

The coating compositions of this invention can be applied to a surfaceto be treated by conventional coating techniques such as, for example,dip coating, direct roll coating, reverse roll coating, curtain coating,spray coating, brush coating, and combinations thereof

The curing of the composition begins when flexibilizer (i), activehydrogen-containing resin (ii), curing agent (vi) and optionalcomponents are mixed together. The curing can be accelerated by using acatalyst. The curing can occur at room temperature. However, the curingrate will increase if the composition is heated to temperatures of from30° C. to 200° C., more specifically of from 70° C. to 140° C.

When active hydrogen-containing resin (ii) also contains an alkoxysilylgroup, the composition has a dual cure, where the alkoxysilyl groupscure by exposure to moisture (water) at temperatures ranging from −10°C. to 200° C. at sub-atmospheric, atmospheric or supra-atmosphericpressures. Generally, moisture content in the air of from 15 to 100percent relative humidity and more advantageously from 30 to 90 percentrelative humidity provides acceptable cure times.

The cured resin composition of the invention is highly suitable forapplication as an adhesive, for example, a windshield adhesive, sealant,coating, gasket, addition to industrial rubber good, and the like.

Various features of the invention are illustrated by the examplespresented below.

EXAMPLES

Preparation of flexibilizer (i) is described below.

Water (600 g) was heated to 85° C. in a 2 L, 3-necked flask equippedwith a reflex condenser, stirrer, addition funnel and a heating mantle.With the stirrer running, a pre-mixed solution of 150 g Me₂SiCl₂, 50 gPh₂SiCl₂ and 90 g toluene was slowly added to the flask. The temperatureof the reaction mixture in the flask was maintained between 75 and 90°C. during addition. The reaction mixture was heated and mixed for anadditional hour at 85° C. Stirring was then discontinued and thereaction mixture allowed to phase separate. The aqueous phase wasdrained, and 200 g of water were added to the organic phase which wasthen heated to 85° C. with stirring. The reaction mixture was heated andmixed for an additional hour at 85° C. Stirring was then discontinuedand the reaction mixture allowed to phase separate. The aqueous phasewas drained, and another 200 g of water were added to the organic phasewhich was then heated to 85° C. with stirring. The reaction mixture washeated and mixed for an additional hour at 85° C. Stirring was thendiscontinued and the reaction mixture allowed to phase separate. Theaqueous phase was drained. The organic phase was stripped for 1 hour at120° C. under 50 mm Hg pressure. The stripped organic phase wascollected as Flexibilizer A, which has the structureHO—Si(CH₃)₂—O—[Si(CH₃)₂O]_(m)—[Si(Ph)₂O]_(n)—Si(CH₃)₂—OH where m/n is4.42.

Preparation of Active Hydrogen-Containing Resin (ii)

Preparation of acrylic polymer #1 as active hydrogen-containing resin(ii) is described below.

Xylene (205.6 grams) and toluene (126.6 grams) were added into a 2 literround bottomed 3-necked flask. One neck of the flask was connected to aU tube which is connected to a water condenser and a temperature probewith nitrogen. The second neck of the flask was connected to amechanical stirrer having a Teflon shaft and blade. The third neck ofthe flask was attached to a 500 ml addition funnel.

The materials listed in Table 1 were mixed in a 1 liter bottle, and thentransferred to the addition funnel.

TABLE 1 Materials wt/gm Styrene monomer 121.3 Methyl methacrylate 117.3Isobornyl methacrylate 117.3 Butyl acrylate 54.6 Ethylhexylacrylate 54.5Hydroxy propyl acrylate 60.5 AIBN (2,2′Azobis(2-methylpropionitrile)30.1

Mixture of xylene and toluene was heated to its reflux temperature. Thenmaterials listed in Table 1 were added drop wise from the additionfunnel to the flask at a uniform addition rate of 2.5 gram per minuteover a 4 hour period. The temperature within the flask was maintained atreflux temperature.

The materials listed in Table 2 were mixed in a 1 liter bottle, and thentransferred to the addition unreel after the addition of materialslisted in Table 1.

TABLE 2 Materials wt/gm AIBN (2,2′Azobis(2-methylpropionitrile) 1.8Xylene 18.8 Toluene 11.5 Triethyl Ortho Formate 10.0

The materials listed in Table 2 were added drop wise from the additionfunnel to the flask at a uniform addition rate of 1.5 grams per minuteover a 30 minutes period. The temperature within the flask wasmaintained at 130° C. for additional 30 minutes, then cooled down toroom temperature. The mixed solvent of xylene and toluene contained 64%solid acrylic polymer #1.

Preparation of acrylic polymer #2 as active hydrogen-containing resin(ii) is described below.

Xylene (205.6 grams) and toluene (126.6 grams) were added into a 2 literround bottomed 3-necked flask. One neck of the flask was connected to aU tube which is connected to a water condenser and a temperature probewith nitrogen. The second neck of the flask was connected to amechanical stirrer having a Teflon shaft and blade. The third neck ofthe flask was attached to a 500 ml addition funnel.

The materials listed in Table 3 were mixed in a 1 liter bottle, and thentransferred to the addition funnel.

TABLE 3 Materials wt/gm Styrene monomer 121.3 Methyl methacrylate 117.3Isobornyl methacrylate 117.3 Butyl acrylate 54.5 Ethylhexylacrylate 54.5Hydroxy propyl acrylate 60.5 Gamma-methacryloxypropyltrimethoxysilane80.1 AIBN (2,2′Azobis(2-methylpropionitrile) 30.1

Mixture of xylene and toluene was heated to its reflux temperature. Thenmaterials listed in Table 3 were added drop wise from the additionfunnel to the flask at a uniform addition rate of 2.5 gram per minuteover a 4 hour period. The temperature within the flask was maintained atreflux temperature.

The materials listed in Table 4 were mixed in a 1 liter bottle, and thentransferred to the addition funnel after the addition of materialslisted in Table 3.

TABLE 4 Materials wt/gm AIBN (2,2′Azobis(2-methylpropionitrile) 1.8Xylene 18.8 Toluene 11.5 Triethyl Ortho Formate 10.0

The materials listed in Table 4 were added drop wise from the additionfunnel to the flask at a uniform addition rate of 1.5 g/min over a 30minutes period. The temperature within the flask was maintained at 130°C. for additional 30 minutes, then cooled down to room temperature. Themixed solvent of xylene and toluene contained 66% solid acrylic polymer#2.

Preparation of rheological additive #1 is described below.

Acrylic polymer #1 (15.7 grams) was added to a 200 ml plastic beaker.Then 2.0 grams of Aerosil R812 (fumed silica) and 13.7 grams of N-butylacetate were added drop wise over 15 minutes. After all materials wereadded to the beaker, a Cowles blade, under low shear speed conditions,was used to create the agitation necessary to mix the materials togetherfor approximately 10 minutes. Then zirconium grind beads were added tothe beaker to grind the fumed silica into the acrylic polyol to a HegmanFineness of 6.0. This procedure took approximately 30 minutes.Afterwards, the mixture was filtered through a nylon mesh which removedthe rheological additive #1 from the zirconium grind beads.

Preparation of rheological additive #2 is described below.

Acrylic polymer #2 (15.1 grams) was added to a 200 ml plastic beaker.Then 2.0 grams of Aerosil R812 (fumed silica) and 13.7 grams of n-butylacetate were added drop wise over 15 minutes. After all materials wereadded to the beaker, a Cowles blade, under low shear speed conditions,was used to create the agitation necessary to mix the materials togetherfor approximately 10 minutes. Then zirconium grind beads were added tothe beaker to grind the fumed silica into the acrylic polyol to a HegmanFineness of 6.0. This procedure took approximately 30 minutes.Afterwards, the mixture was filtered through a nylon mesh which removedthe rheological additive #2 from the zirconium grind beads.

Preparation of Catalyst Solution #1 is described below.

n-Butyl acetate (9.5 grams) and dibutyl tin dilaurate (0.5 grams) wereadded to a 50 ml plastic beaker. Once all the materials were added, slowagitation was employed to ensure full dissolution of all materials.

Preparation of curing agent (vi) is described below.

Desmodur N3300 (100.00 grams, available from Bayer), 111.11 grams ofVestanat T1890 (available from Evonik Industries), and 3.33 grams ofn-butyl acetate were added to a 250 ml beaker using a stirring bladeunder slow agitation. Once all materials were incorporated, thematerials were allowed to mix under medium agitation for an additional30 minutes to ensure full dissolution of all materials.

Preparations of coating compositions are described below.

The materials used to prepare coating compositions are shown in Table 5below. Tinuvin 328 and Tinuvin 292 are available from BASK. CoatOSil2816 is available from Momentive Performance Materials Inc.

TABLE 5 Material/Solution Wt (gms) Example 1 Comparison 1 Comparison 2Flexibilizer (i) 7.00 0 0 Acrylic Polymer #1 — 152.28 — Acrylic Polymer#2 146.30 — 146.30 Rheology Additive #1 — 9.42 — Rheology Additive #29.24 — 9.24 Tinuvin 328 3.00 3.00 3.00 Tinuvin 292 1.00 1.00 1.00CoatOSil 2816 0.10 0.10 0.10 Catalyst Solution #1 5.00 5.00 5.00 n-ButylAcetate 30.00 30.00 30.00 Methyl Ethyl Ketone 25.00 25.00 25.00 Curingagent (vi) 19.60 18.14 16.52

Materials listed in Table 5 with the exception of curing agent (vi) wereadded to a 250 ml beaker using a stirring blade under slow agitation.Then, curing agent (vi) was added to the beaker. Once all materials wereadded, the compositions were allowed to mix under medium agitation foran additional 30 minutes to ensure full dissolution of all materials.

Cleaning and Preparation of Cold Roll Steel Panels

The substrates used for testing were Cold Roll Steel APR10184 panelsavailable from ACT Test Panels. A cleaning solution was prepared bemixing Triton X-100 (0.06 weight percent, available from Aldrich),sodium metasilicate (anhydrous, 0.52 weight percent, available fromAldrich), sodium carbonate (anhydrous, 0.49 weight percent, availablefrom Aldrich), sodium phosphate, dibasic (anhydrous, 0.35 weightpercent, available from Aldrich) and de-ionized water (98.57 weightpercent). The clean solution was heated to a temperature of from 65° C.to 70° C. The Cold Roll Steel panels were immersed in heated and stirredcleaning solution for 2 to 3 minutes to remove any oil contaminants. Thepanels were then removed from the solution and immediately rinsed withde-ionized water. Kimwipe Kimtech Delicate Task Wipers, available fromKimberly Clark, were used to wipe the panels dry. The panels were thenlightly sprayed with water to determine the water break of the cleanedpanels. If the panels showed water beading, then the cleaning processwas repeated. If the water formed a continuous sheen, then the panelswere then dried with a Kimwipe wiper and stored for use in a desiccantchamber.

Procedure for Spray Application

Each coating composition was spray applied over cleaned metal panelswhich were cut into 2-inch by 4-inch (5.08-centimeter by10.16-centimeter) dimensions. Spray application was conducted with aStarting Line High Volume Low Pressure gravity fed siphon spray handheld spraygun, available through DeVilbiss. The coating compositionswere sprayed at a gauge pressure near the gun of 25 lb/in² (172kilopascal). The spray application technique was a side-to-side sweep ofthe spray onto the panel at a rate of approximately 800 inch per minute(20 meters per minute), indexing up and down the panels at approximately1 inch (2.54 centimeters) per sweep. Several panels were preparedsimultaneously and one entire pass along the entire panel set wouldencompass approximately 5 to 6 sweeps. Each set of panels was preparedto have about 3.5 to 4.5 mils (88.9 to 114.3 microns) dry filmthickness, of each coating formulation.

Procedure for Panel Curing

One set of the spray applied coating composition was cured at ambientconditions while another set from the same spray applied coatingcomposition was flash dried at ambient conditions for a period no lessthan 15 minutes, but no more than 40 minutes, then cured for 30 minutesat 250° F. (121° C.). These cure procedures were repeated for the otherpanels as well. Both panel sets were then conditioned for approximately6 days before additional testing began.

Procedure for Panel Flexibility Testing

After approximately six days of ambient conditioning, the panels, fromboth sets, were placed into an oven for thermal conditioning at 80° C.(176° F.) for approximately 60 hours. After removal from the oven, thecoated panels were allowed to cool to room temperature before beingsubjected to Conical Mandrel bending. Average dry film thicknesses werebetween ˜3.9±0.3 mils (˜99 microns).

Mandrel Bending was performed in accordance with ASTM-D522 atapproximately 1¼″ to 1½″ conical diameter with average bend diameter of1 and ⅜″-inch (3.49 centimeter) diameter bend section of the instrument.The flexibility results on conical mandrel bend were shown in Table 6.The panels were rated either as a PASS, where the samples showed noevidence of cracking after bending, or a FAIL, where the panel showedevidence of multiple cracks and/or delamination. DCU2010 and DCX2011 areavailable from PPG Industries.

TABLE 6 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) Room PASSED FAILED FAILED PASSED Temperature CureSevere Severe for ~6 days week Cracking Cracking followed by ~60 hrs @80° C. Flashed l hr, then PASSED FAILED FAILED PASSED Cured for SevereSevere 30 minutes at Cracking Cracking 250° F., followed by ambientstorage for ~6 days, followed by ~60 hrs @ 80° C.

Procedure for Measuring Coated Panel Gloss

House of Kolor SB-26 white base available from Valspar was spray appliedon panels prior to the application of clear coat.

Gloss measurements were carried out in accordance with ASTM D523 oncoated panels. Gloss was measured using a Byk-Gardner micro-TRIGlossmeter.

CIE L*a*b* Color, daylight at the 65° angle (D65), measurements weretaken using a Konica Minolta CR-400 colorimeter set up for automaticallytaking 3 sample measurements, then averaging the result for color on theL*a*b* scale. QUV-B accelerated weathering results on ambient curedpanels and 60° gloss results as a function time in QUV-B are shown inTable 7.

TABLE 7 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) Initial 60° C. 90.2 91.5 89.0 90.3 Gloss 60° C.Gloss 93.0 94.2 93.8 93.8 after 30 Days

Procedure for QUV-B Testing

House of Kolor SB-26 white base available from Valspar was spray appliedon panels prior to the application of clear coat.

The Accelerated Weather Chamber used was a Q-Panel Company, Q-U-VAccelerated Weathering Tester, 26200 First St. Cleveland, Ohio 44145.

The bulbs used were for QUV-B testing and the Weathering test was setfor an entire 24 hour cycle of QUV-B light. QUV-B accelerated weatheringresults on ambient cured panels and ΔE color change as a function oftime in QUV-B are shown in Table 8.

TABLE 8 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) ΔE Color 2.77 3.47 2.96 13.01 Change after 30 Days

Procedure for Pendulum Hardness Testing

Pendulum Hardness measurements were carried out on the coated panels.The Konig pendulum apparatus was used and the motion of swing began atthe 12° angle. This provided greater surface hardness resolution of thecoated panels. Pendulum hardness measurements after seven days are shownin Table 9. Pendulum hardness measurements after fourteen days are shownin Table 10. Pendulum hardness measurements after twenty eight days areshown in Table 11.

TABLE 9 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) Room 105 88 84 59 Temperature Cured for ~7 daysFlashed l hr, then 219 215 218 201 Cured for 30 minutes at 250° F.,followed by ambient storage for ~7 days

TABLE 10 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) Room 137 107 102 71 Temperature Cured for ~14 daysFlashed l hr, then 228 207 220 213 Cured for 30 minutes at 250° F.,followed by ambient storage for ~14 days

TABLE 11 Comparison 3 (DCU2010/ Conditioning Example 1 Comparison 1Comparison 2 DCX2011) Room 157 113 120 93 Temperature Cured for ~28 daysFlashed l hr, then 235 218 235 222 Cured for 30 minutes at 250° F.,followed by ambient storage for ~28 days

The harder the surface of the film, the higher the number of pendulumswings, and the higher the number of swing counts. The softer the filmwas, the lower the number of swing counts (cycles).

Procedure for Sulfuric Acid Etch Testing

A solution of 10% wt concentration of sulfuric acid was prepared fordetermining clearcoat acid etch resistance as a function of temperature.A drop of this solution was placed onto each panel and then placed intoan oven beginning at 30° C. After 20 minutes in the oven, the coatedpanels were removed, wiped dry and allowed to cool. The coated panelswere then checked for acid etch markings caused by the chemical attackof the sulfuric acid on the coated surface. The oven temperature wasraised incrementally by 5° C., and the drop test was repeated in asimilar fashion on the coated panels until a maximum temperature of 70°C. was reached. The temperature at which etching occurred is shown inTable 12. Resultant temperature leaving no etch mark on coating surface.

TABLE 12 Comparison 3 Example Comparison Comparison (DCU2010/Conditioning 1 1 2 DCX2011) Panels cured 30 55° C. 50° C. 50° C. 40° C.minutes @ 250° F.

These data indicate that the composition of Example 1 containing theflexibilizer (i) provided for improved flexibility (Passed) and hardness(105) when cured at room temperature for 7 days, as compared to asimilar composition, Comparison 2, which failed the flexibility and hada hardness of only 84, or the commercial coating, Comparison 3, whichpassed the flexibility but had a hardness of only 59.

These examples are to be construed as exemplary in nature only and arenot intended in any way to limit the appended claims. It is contemplatedthat a person having ordinary skill in the art would be able to produceobvious variations of the subject matter and disclosures hereincontained that would be by reason of such ordinary skill within theliteral or equitable scope of the appended claims.

What is claimed is:
 1. A composition comprising: (a) flexibilizer (i)having the general formula (I):

wherein: each occurrence of R¹ is independently an alkyl group havingfrom 1 to 6 carbon atoms, a phenyl group or an arenyl group having 7 to12 carbon atoms; each occurrence of R² is independently an alkyl grouphaving from 1 to 6 carbon atoms; each occurrence of R³ is independentlya phenyl group or an arenyl group having 7 to 12 carbon atoms; eachoccurrence of X¹ is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, or an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group; eachoccurrence of X² is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group, or agroup with the formula (II):

wherein: R¹, R² and R³ are the same as defined above; each occurrence ofsubscripts a, b, c, d, e and f is independently an integer wherein a is1 to 3; b is 0 to 500, c is 1 to 500, d is 0 to 10, e is 0 to 50, and fis 0 to 50 with the provisos that (1) the molar ratio of b to c is from0:1 to 15:1, and (2) the molar ratio of d to c is from 0:1 to 1:1; (b)at least one active hydrogen-containing resin (ii); and, (c) at leastone curing agent (vi) selected from the group consisting ofisocyanate-containing compound (vii), blocked isocyanate-containingcompound (viii) and aminoplast (ix).
 2. The composition of claim 1wherein each occurrence of X¹ is independently hydroxyl, methoxy,ethoxy, propoxy or isopropoxy; R¹ is methyl or phenyl; R² is methyl; R³is phenyl; b is 1 to 100; c is 2 to 100; d is 0; and the molar ratio ofb to c is from 1:1 to 10:1.
 3. The composition of claim 1 whereinflexibilizer (i) has a silanol content or a SiX¹ content of from 2 to 15mole %, based upon the total number of silicon atoms.
 4. The compositionof claim 1 wherein flexibilizer (i) has a weight average molecularweight of from 500 to 50,000.
 5. The composition of claim 1 whereinflexibilizer (i) isHO—Si(CH₃)₂—O-[Si(CH₃)₂O]_(r)—[Si(Ph)₂O]_(s)—Si(CH₃)₂—OH where r/s is 4,CH₃O—Si(CH₃)₂—O—[Si(CH₃)₂O]_(u)—[Si(Ph)₂O]_(w)Si(CH₃)₂—OCH₃ where u/w is3, Ph is phenyl, or mixtures thereof.
 6. The composition of claim 1wherein active hydrogen-containing resin (ii) is at least one memberselected from at least one member of the group consisting of polyol(iii), amine-functional resin (iv), and mercapto-functional resin (v).7. The composition of claim 6 wherein polyol (iii) is at least onemember selected from the group consisting of acrylic polyol, polyetherpolyol, polyester polyol, polyetherester polyol, hydroxyl-terminatedpolybutadiene, hydroxyl-terminated polyurethane, polyesterether polyoland acrylic polyol containing a alkoxysilyl group, and mixtures thereof.8. The composition of claim 1 wherein polyol (iii) is acrylic polyolcontaining an alkoxysilyl group and the curing agent (vi) is apolyisocyanate.
 9. The composition of claim 6 wherein amine-functionalresin (iv) is represented by general formula (VI):[H(R⁹)N-]_(g)R¹⁰  (VI) wherein R⁹ is hydrogen, a linear, cyclic orbranched hydrocarbon group having from 1 to 18 carbon atoms, which isoptionally substituted by heteroatoms, an alkyl radical which isinterrupted by nonadjacent oxygen atoms, an alkoxy group —OR¹¹ or anacyloxy group —O—C(═O)—R¹² wherein R¹¹ is hydrogen or a linear, cyclicor branched hydrocarbon group having from 1 to 18 carbon atoms and R¹²is a hydrogen or a hydrocarbon contain from 1 to 18 carbon atoms; R¹⁰ isa linear or branched polymer group having a number average molecularweight of from 500 to 25,000, as determined in accordance with DINStandard 55672 (1) using polystyrene standards; and g is an integer ofgreater than
 1. 10. The composition of claim 6 whereinmercapto-functional resin (v) is represented by general formula (VII):R¹³SH)_(h)  (VII) wherein R¹³ is a linear or branched polymer grouphaving a number average molecular weight of from 500 to 25,000, asdetermined in accordance with DIN Standard 55672 (1) using polystyrenestandards; and, h is an integer greater than
 1. 11. The composition ofclaim 1 wherein curing agent (vi) is an isocyanate containing compound(vii) selected from at least one member of the group consisting of1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4- and2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, omega,omega′-diisocyanatodipropyl ether, cyclobutane1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 2,2- and2,6-diisocyanato-1-methylcyclohexane,3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 2,5- and3,5-bis(isocyanatomethyl)-8-methyl-1,4-methano-decahydronaphthalene,1,5-, 2,5-, 1,6- and2,6-bis(isocyanatomethyl)-4,7-methanohexahydroindane, 1,5-, 2,5-, 1,6-and 2,6-bis(isocyanato)-4,7-methylhexahydroindane, dicyclohexyl2,4- and4,4′-diisocyanate, and 2,6-hexahydrotolylene diisocyanate, perhydro2,4′- and 4,4′-diphenylmethane diisocyanate,omega,omega′-diisocyanato-1,4-diethylbenzene, 1,3- and 1,4-phenylenediisocyanate, 4,4′-diisocyanatobiphenyl,4,4′-diisocyanato-3,3′-dichlorobiphenyl,4,4′-diisocyanato-3,3′-dimethoxybiphenyl,4,4′-diisocyanato-3,3′-dimethylbiphenyl,4,4′-diisocyanato-3,3′-diphenylbiphenyl, 2,4′- and4,4′-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, 2,4- and2,6-tolylene diisocyanate,N,N′-(4,4′-dimethyl-3,3′-diisocyanatodiphenyl)uretdione, m-xylylenediisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylenediisocyanate, 2,4,4′-triisocyanatodiphenyl ether,4,4′,4″-triisocyanatotriphenyl methane consisting of toluene2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane4,4′-diisoyanate, diphenylmethane 2,4′-diisocyanate, p-phenylenediisocyanate, biphenyl diisocyanates, 3,3′-dimethyl-4,4′-diphenylenediisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, isophoronediisocyanate, ethylene diisocyanate, dodecane 1,12-diisocyanate,cyclobutane 1,3-diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane1,4-diisocyanate, methylcyclohexyl diisocyanates, hexahydrotoluene2,4-diisocyanate, hexahydrotoluene 2,6-diisocyanate, hexahydrophenylene1,3-diisocyanate, hexahydrophenylene 1,4-diisocyanate,perhydrodiphenylmethane 2,4′-diisocyanate, 4,4′-methylenedicyclohexyldiisocyanate, tetramethylxylyl diisocyanates, biuret dimers and theisocyanurate trimers thereof.
 12. The composition of claim 1 containingfrom 1.0 to 98 percent by weight active hydrogen-containing resin (ii)based on the total weight of the composition, from 0.1 to 80 parts byweight flexibilizer (i) based on one hundred parts of activehydrogen-containing resin (ii), and from 0.1 to 90 parts by weightcuring agent (vi) based on one hundred parts of activehydrogen-containing resin (ii).
 13. The composition of claim 1, furthercomprising at least one additional component (xi) selected from at leastone member of the group consisting of catalyst, organic solvent,polysiloxane resin other than formula (I), isocyanate-reactivescavenging agent, water scavenger agent, desiccant, non-silicon-basedepoxy hardener, surfactant, colorant, rheology modifier, plasticizer,extender, filler, reinforcing agent, adhesion promoter, hydrocarbonresin modifier, UV stabilizer, wetting agent, flow and levelingadditive, thixotrope and defoamer.
 14. The composition of claim 13,wherein the catalyst is at least one member selected from the groupconsisting of organic tin, zirconium complex, aluminum chelate, titanicchelate, organic zinc, organic cobalt, organic iron, organic nickel andorganobismuth, amine catalyst, dibutyltin oxide, dimethyltin diacetate,dimethyltin dilaurate, dimethyltin dineodecanote, dibutyltin dilaurate,dioctyltin dilaurate, dibutyltin diacetate, stannous octoate, stannousacetate, stannous oxide, morpholine, tri-isopropylamine,bis-(2-dimethylaminoethyl) ether and piperazine.
 15. The composition ofclaim 13 wherein the filler is at least one member selected from thegroup consisting of particulate metal, fumed metal oxide, precipitatedmetal oxide, precipitated and ground metal carbonate and carbon black,metal sulfate, metal phosphate, silicate, and having a concentration inthe range of from 0 to 50 weight percent based on the total weight ofcomponents (i), (ii), (vi) and filler.
 16. The composition of claim 13wherein the plasticizer is liquid organic compound selected from atleast one member of the group consisting of alkyl phthalate, alkylsulphate and polyether, alkyl acrylate, and having a concentration inthe range up to 40 parts by weight per hundred parts of activehydrogen-containing resin (ii).
 17. The composition of claim 13 whereinthe water scavenger agent is an alkoxysilane selected from at least onemember of the group consisting of vinyltrimethoxysilane andmethyltrimethoxysilane, and having a concentration in the range up to 5percent by weight, based on the weight of active hydrogen-containingresin (ii).
 18. The composition of claim 13 wherein the adhesionpromoter is an organofunctional alkoxysilane, and having a concentrationin the range up to 5 percent by weight, based on the weight of activehydrogen-containing resin (ii).
 19. The composition of claim 1 whereinthe composition is an adhesive, a sealant, a composite or a coating. 20.The cured composition of claim
 1. 21. A substrate comprising the curedcomposition of claim
 20. 22. A substrate having the composition of claim1 applied thereto.
 23. A composition comprising: (a) flexibilizer (i)having the general formula (I):

wherein: each occurrence of R¹ is independently an alkyl group havingfrom 1 to 6 carbon atoms, a phenyl group or an arenyl group having 7 to12 carbon atoms; each occurrence of R² is independently an alkyl grouphaving from 1 to 6 carbon atoms; each occurrence of R³ is independentlya phenyl group or an arenyl group having 7 to 12 carbon atoms; eachoccurrence of X¹ is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, or an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group; eachoccurrence of X² is independently a hydroxyl group, an alkoxy grouphaving from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6carbon atoms and at least one ether or ester functional group, or agroup with the formula (II):

wherein: R¹, R² and R³ are the same as defined above; each occurrence ofsubscripts a, b, c, d, e and f is independently an integer wherein a is1 to 3; b is 0 to 500, c is 1 to 500, d is 0 to 10, e is 0 to 50, and fis 0 to 50 with the provisos that (1) the molar ratio of b to c is from0:1 to 15:1, and (2) the molar ratio of d to c is from 0:1 to 1:1; and,(b) flexibilizer-reactive component (x).
 24. The composition of claim 23wherein flexibilizer-reactive component (x) is at least one memberselected from the group consisting of filler, resin containingsilanol-reacting group and resin containing alkoxy-reacting group. 25.The composition of claim 24 wherein the filler is at least one memberselected from the group consisting of particulate metal, fumed metaloxide, precipitated metal oxide, precipitated and ground metal carbonateand carbon black, metal sulfate, metal phosphate, silicate, and having aconcentration in the range up to 50 weight percent based on the totalweight of composition.
 26. The composition of claim 23 wherein thecomposition is an adhesive, a sealant, a composite or a coating.
 27. Thecured composition of claim
 23. 28. A substrate comprising the curedcomposition of claim
 27. 29. A substrate having the composition of claim23 applied thereto.